Born in 1888, Asaf Ali was educated at St Stephen's College, Delhi, and then went to London to study law in 1909. Asaf Ali was a frequent visitor to India House in Highgate, having been met by a resident at Charing Cross. He became close friends with Virendranath Chattopadhyaya (Chatto) and met Madame Cama in Paris. After a couple of weeks of lodging in India House, he then moved to lodgings in Finsbury Park and studied for the Bar at Lincoln's Inn. Just as Jawaharlal Nehru remembers that he did not visit India House during his time as a student, Asaf Ali recalls that he did not meet Nehru when he was studying for the Bar although they were in London at the same time. Asaf Ali was in London when Syed Ameer Ali founded the London Muslim League and attended the Universal Races Congress in London in 1911. He was called to the Bar in January 1912 and returned to India to practice.

In 1914, Asaf Ali returned to England on a Privy Council Brief. Upon his return he met up with old friends and began to frequent the National Liberal Club. He planned a publication of an Urdu literary magazine called Taj from London but the costs were beyond his means. He translated some of Rabindranath Tagore's poems into Urdu and was then introduced to Tagore at a reception at the Criterion organized by Indian residents in London. Having been friends with Chatto, he was introduced to Sarojini Naidu, his sister, and decided to organize a literary dinner for Naidu. He invited a whole host of famous British literary figures and invited W. B. Yeats to chair and propose the toasts. Ali and Naidu would often visit the Poetry Bookshop where Harold Monro organized readings.

In 1914, the British attack on the Ottoman Empire had a large effect on the Indian Muslim community. Asaf Ali supported the Turkey side and resigned from the Privy Council. He saw this as an act of non-cooperation and returned to India in December 1914. Upon his return to India, Asaf Ali became heavily involved in the nationalist movement. He was elected to the Central Legislative Assembly in 1935 as a member of the Muslim Nationalist Party, but then became a prominent member of Congress and was chosen as deputy leader. He was imprisoned in Ahmadnagar in 1944. His wife, Aruna, whom he married in 1928 and was of Hindu background, was a prominent Congress nationalist and socialist.

In 1947, Asaf Ali was appointed Ambassador to the United States, was Governor of Orissa from 1948 to 1952 and was then India's Minister to Switzerland, Austria and the Vatican. He died in 1953 in Switzerland.