Soon De Morgan began experimenting with stained glass, ventured into pottery in 1863, and by 1872 had shifted his interest wholly to ceramics, initially working in Fitzroy Square.

Dust pressed tiles of white earthenware were bought from Wedgwood, Mintons and other manufacturers but De Morgan believed these would not stand frost.

His inventive streak led him to spend hours designing a duplex bicycle gear and lured him into complex studies of the chemistry of glazes, methods of firing, and pattern transfer.

Around 1873–1874, he made a striking breakthrough by rediscovering the technique of lustreware (marked by a reflective, metallic surface) found in Hispano-Moresque pottery and Italian maiolica.

As early as 1875, he began to work in earnest with a "Persian" palette: dark blue, turquoise, manganese purple, green, Indian red, and lemon yellow.

[citation needed] The pottery works was beset by financial problems, despite repeated cash injections from his wife, the pre-Raphaelite painter Evelyn De Morgan (née Pickering), and a partnership with the architect Halsey Ricardo.

During the Fulham period De Morgan mastered many of the technical aspects of his work that had previously been elusive, including complex lustres and deep, intense underglaze painting that did not run during firing.

However, this did not guarantee financial success, and in 1907 De Morgan left the pottery, which continued under the Passenger brothers, the leading painters at the works.

Recollections praise him for his personal warmth and the indomitable energy with which he pursued his kaleidoscopic career as designer, potter, inventor and novelist.

The National Gallery of Canada in Ottawa has a good collection of William De Morgan's work given by Ruth Amelia Jackson in 1997 but much of it is kept in store.