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The calmly-assured quality of George Knapton's sitter, and her colourful draperies are a legacy both of the painter's training between 1715 and 1722 under Jonathan Richardson, who provided one of the most solid artistic schoolings for a portraitist at that time, and the influence of the St Martin's Lane Academy, which the painter attended in 1720, other painters in whose orbit -Hogarth and Hayman for example- display the same interest in clear, bright pigments. Characteristic of Knapton himself at this date is the careful delineation of lacework in thick white lead.

Knapton was a founder-member of the Roman Club (1723), a society of literary men and artists with aspirations to connoisseurship. In 1725 he travelled to Italy, as did Arthur Pond and other members of the Club around this time; Knapton seems to have been the only member to study painting while abroad. He became acquainted with many Grand Tourists and, after his return to London in 1732, he was a founder-member of the Society of Dilettanti whose first official portrait painter he became in 1740 and remained until 1763. Between 1741 and 1749 he produced a series of members' portraits, many wearing fancy dress, demonstrating again Knapton's preoccupation with colour, and a number of these portraits remain in the Society's possession.

Following his return to London, Knapton made good use of his contacts in order to obtain portrait commissions; these he did mostly in pastel, then a fashionable innovation. In 1743 George Vertue included Knapton in his list of the best available painters and in 1750 thought his style much improved. Knapton lacked the necessary grand manner, however, and was never successful in large-scale compositions.

In 1740 Knapton returned briefly to Italy; while there he inspected the excavations at Herculaneum, describing his visit in a letter to Pond that was published in the Royal Society's Philosophical Transactions the same year. His reputation for connoisseurship was further enhanced by his participation in the family firm run by John Knapton and Paul Knapton, who were probably his cousins. Together with his brother Charles Knapton (1700-60), an engraver and landscape painter, and Arthur Pond, he furnished drawings and engravings for several of the firm's publications, notably Birch's Lives and Characters of Eighty Illustrious Persons of Great Britain (London, 1742-51), the portrait heads for which were engraved by Jacobus Houbraken. In 1746 Knapton was employed to make an inventory of the collection of John, 1st Earl Spencer, and in 1750 he accompanied Vertue on an inspection of the royal collections held at Kensington and Hampton Court palaces, London, and Windsor Castle, at the request of Frederick, Prince of Wales, who sought for his own use a detailed and critical catalogue. By the early 1760s Knapton had given up painting. In 1765 his abilities as a connoisseur were officially recognized when he succeeded Stephen Slaughter as Surveyor to the King's Pictures, a post he retained until his death.