Photorespiration is a primary metabolic pathway, which, given its energy costs, has often been viewed as a wasteful process. Despite having reached the consensus that one important function of photorespiration is the removal of toxic metabolite intermediates, other possible functions have emerged, and others could well emerge in the future. As a primary metabolic pathway, photorespiration interacts with other routes; however the nature of these interactions is not well known. One of these interacting pathways could be the biosynthesis of serine, since this amino acid is synthesised through photorespiratory and non-photorespiratory routes. At present, the exact contribution of each route to serine supply in different tissues and organs, their biological significance and how pathways are integrated and/or regulated remain unknown. Here, we review the non-photorespiratory serine biosynthetic pathways, their interactions with the photorespiratory pathway, their putative role in plants and their biotechnological interest.