The pictures at Ascott reflect the passion for collecting of the Rothschilds over three generations. The key figures are Lionel de Rothschild, the eldest of the second generation English Rothschilds, his youngest son and the builder of Ascott, Leopold and his grandson, Anthony, who gave the collection to the National Trust.

Lionel bought mainly 17th and early 18th century Dutch and Flemish cabinet pictures. He also bought glamorous full length portraits of 18th century beauties by Reynolds and Gainsborough. Lionel patronised modern artists to a lesser extent. On his death in 1879 Lionel left instructions that his three sons should choose pictures for themselves in turn. Therefore, Ascott only has a small part of the original collection.

Anthony de Rothschild added to the picture collection but his main interest was in Chinese ceramics which he collected during the 1920s and 1930s. His interest may have stemmed from a visit to China in 1911 and from the vogue for collecting Chinese wares in the following years. The collection partly reflects the fashion of the time but includes many pieces only appreciated by connoisseurs.

The furniture is a mixture of 18th century English and French styles. The French pieces were inherited by Leopold de Rothschild from his father while the English collection was assembled by Anthony de Rothschild and his wife, Yvonne.