Vitamin C (Vc) is a relatively abundant small molecule in both animal and plant cells and plays many important roles in growth and development of animals and plants. In this paper, we review studies of Vc biosynthesis and metabolism conducted with the model plant Arabidopsis thaliana. Related investigations in crop species, although much less advanced than those reported in Arabidopsis, are also summarized. The information will be useful for further studies of Vc biosynthesis and metabolism to improve stress tolerance and nutritional quality of important crops through molecular breeding.