The younger daughter of Ford Madox Brown by his second wife Emma Hill, Catherine was born on 11 November 1850 but her parents did not marry until April 1853. Like her elder sister Lucy and younger brother Oliver, she studied painting with her father, and for a few years from 1869 exhibited at the Royal Academy, the Dudley Gallery and elsewhere. At different ages she also posed for several of her father's pictures, appearing as the baby in Pretty Baa Lambs (1851-59; Birmingham), the child eating an apple in The Last of England (1855; Birmingham), the little girl in Stages of Cruelty (1856-90; Manchester), and the grown-up girl in The Nosegay (1865; Ashmolean Museum, Oxford). A talented pianist, she married the music critic Dr Franz Hueffer in 1872, and the novelist Ford Madox Hueffer (later Ford) was their child.

At the Opera was the first of three works she showed at the Royal Academy, appearing, as the label on the back notes, the year it moved from the National Gallery building in Trafalgar Square to Burlington House, Picadilly. 'Cathy is very well hung, and looks magnificent.' her father wrote fondly at the time (F.M. Hueffer, Ford Madox Brown, 1896, p.252). The picture clearly betrays his influence, but is also an example of the early 'aesthetic' style practised by so many of the younger 'Pre-Raphaelites' who exhibited at the Dudley Gallery, forerunner of the Grosvenor, in the late 1860s. The model may be the artist's sister Lucy; compare D.G. Rossetti's portrait of her five years later (Virginia Surtees, Dante Gabriel Rossetti. A Catalogue Raisonné, 1971, no.454, pl.417).

Catherine Hueffer's work is rare; the Witt Library has little, mostly family portraits in private hands.