Ann James grew up in Ringwood, Victoria, and was educated at Norwood Primary School and Tintern Girls School.
An illustrator who trained as an arts and crafts teacher, James taught at Doveton and Ringwood High Schools before being seconded to the Publications Branch of the Education Department of Victoria where she worked as a graphic designer and illustrator of educational publications from 1978.
James's involvement with children's books began when she entered a competition with colleague Gwenda Smythe for unpublished authors and illustrators in 1981. The book they entered was A Pet for Mrs Arbuckle and it launched her into a successful career in illustration. James has illustrated for many well known Australian authors and is perhaps best known for her design and illustration of Robin Klein's four Penny Pollard books, which were published between 1983 and 1988. Whilst working with the Penny Pollard books, James found time to illustrate numerous other books, including Bernice Knows Best, by Max Dann, for which she won the Children's Book Council of Australia Junior Book of the Year Award in 1984. She has since had many of her illustrated books shortlisted for awards.
James also co-directs Books Illustrated, a gallery which has year-round exhibitions solely devoted to children's books. There are exhibitions of original illustrations by Australian children's book illustrators, and schools and college groups visit for tours, talks and demonstrations by illustrators. James has also published a book on illustrating, Making Pictures: Techniques for Illustrating Children's Books (with Ann Haddon, 1996).