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Dulwich was formerly part of the ancient parish of Camberwell, which later became the Metropolitan Borough of Camberwell, and included Camberwell, Peckham, Nunhead, and other London districts.

The first documented evidence of Dulwich is as a hamlet outside London in 967AD, granted by King Edgar to one of his thanes Earl Ælfheah. The name of Dulwich has been spelt in various ways, Dilwihs, Dylways, Dullag, and may come from two old English words, Dill, a white flower, and wihs, meaning a damp meadow, giving a meaning of "the meadow where dill grows".

Harold Godwinson owned the land at one point, and after 1066, King William I of England. In 1333, the population of Dulwich was recorded as 100.

In 1538, Henry VIII seized control of Dulwich and sold it to goldsmith Thomas Calton. Calton's grandson Sir Francis Calton sold the Manor of Dulwich in 1605 to Elizabethan actor and entrepreneur Edward Alleyn. He vested his wealth in a charitable foundation, Alleyn's College of God's Gift, established in 1619. The charity's modern successor, The Dulwich Estate, still owns 1,500 acres in the area, including a number of private roads and a tollgate. Alleyn also constructed a school, a chapel and alms houses in Dulwich. Dulwich Almshouse Charity and Christ's Chapel of God's Gift at Dulwich (where Alleyn is buried) still fulfill their original functions.

Alleyn's original school building is no longer used for that purpose, instead now housing the Estate's Governors. The school moved around 1840 to accommodate larger numbers of pupils into new buildings designed by Charles Barry (junior), son of Sir Charles Barry who designed Westminster Palace. It was subsequently divided into Dulwich College and Alleyn's School in 1882, the latter moving to the present day site in Townley Road.

In the 17th century, King Charles I of England visited Dulwich Woods on a regular basis to hunt. In 1738, a man named Samuel Bentyman was murdered in Dulwich Woods.

On 5 August 1677 John Evelyn writes that he took the waters at Dulwich. The Dulwich waters were cried about the streets of London as far back as 1678.

In 1739, Mr. Cox, master of the Green Man, a tavern situated about a mile south of the village of Dulwich, sunk a well for his family. The water was found to be possessed of purgative qualities, and was for some time used medicinally. While the water was popular much custom was drawn to the adjoining tavern, and its proprietor flourished.

The oak-lined formal avenue, known as Cox's Walk, leading from the junction of Dulwich Common and Lordship Lane was cut soon after 1732 by Francis Cox to connect his establishment of the Green Man Tavern and Dulwich Wells with the more popular Sydenham Wells.

By 1815 the Green Man had become a school known as Dr. Glennie's academy in Dulwich Grove, although it was demolished about ten years later. Among the pupils here there were a few who became well known, Lord Byron, General Le Marchant and Captain Barclay.

Dr Glennie held Saturday evening concerts which attracted visitors from outside the family circle, such as the poet Thomas Campbell, then living in nearby Sydenham, and Robert Barker, inventor of the panorama. Following the closure of the school, the building reverted to its original use and was known as the Grove Tavern.

In 1803, Samuel Matthews - known as the "Dulwich Hermit" - was also murdered in Dulwich Woods; he was buried in Dulwich Old Cemetery.

1811-1814 saw the building of the Dulwich Picture Gallery.

There are a number of recognised districts in Dulwich:

• Dulwich Village which includes the traditional village centre;
• East Dulwich which bounds Peckham at Peckham Rye is a separate centre - not just the eastern end of Dulwich - with its own distinct character;
• West Dulwich which is a mainly residential area bordering West Norwood and Tulse Hill;
• Herne Hill (the Southwark half) which forms the North Dulwich Triangle, borders Brixton, Denmark Hill, Loughborough Junction and Tulse Hill;

Dulwich Village contains the original shopping street and still contains nearly all of its original 18th and 19th century buildings. It remains very uncommercialised and is a conservation zone. The village borders on Dulwich Park, where the Dulwich Horse and Motor Show is held every year.

Dulwich Park was opened in 1890. It was formerly farmland, part of the Court Farm, and now offers duck and rowing ponds, children's play area, bowling green, tennis court, bridle path for horse-riding, and café.

Dulwich Hospital in East Dulwich Grove was designed by Henry Jarvis and built on 7 acres of land purchased in East Dulwich by the Guardians of the Poor of the Parish of St Saviour, Southwark in 1885. At the time of opening in 1887, it offered a 723-bed capacity. It was transformed from an infirmary into the Southwark Military Hospital during World War I, when it is estimated 14,000-15,000 wounded soldiers were treated at the hospital. After the Poor Law was abolished in 1930, the Southwark Union Infirmary was renamed Dulwich Hospital and the following year an operating theatre was built. In 1964, the hospital was aligned with King's College Hospital on Denmark Hill. There is no casualty department at Dulwich at present. However, in 2015 it was announced that Dulwich Hospital was to be closed and replaced by a school.

There is a memorial fountain in Dulwich Village which is in remembrance to Dr George Webster, founder of the first British Medical Association (BMA), who worked in Dulwich from 1815 until his death in 1875.

Old Burial Ground, Dulwich Village, was created by Edward Alleyn as part of the foundation of his College of God's Gift. The Archbishop of Canterbury, George Abbot, conducted the consecration on Sunday 1 September 1616. Guests included Edmund Bowyer, Thomas Grimes, William Gresham, Thomas Hunt and Jeremiah Turner. Thirty five Dulwich victims of the plague were buried in unmarked graves in the ground. Old Bridget, queen of the Norwood Gypsies (who appeared in the writings of Samuel Pepys) was also buried here in 1768. The ground was declared "full" in 1858, however the family of Louisa Shroeder obtained special permission for her remains to be interred in 1868. The ground's wrought iron gates and twelve tombs are Grade II listed.

The old Grammar School adjacent to the Old College and Almshouses at the junction of Burbage Road and Gallery Road was designed by Charles Barry (senior).

Famous people born there include the author, Enid Blyton, in 1897.