The majority if not all of the organic nitrogen in plants is derived from the assimilation of ammonia into the amide position of glutamine by the enzyme glutamine synthetase (GS). A second enzyme, glutamate synthase, also known as glutamine:2‐oxoglutarate amidotransferase (GOGAT), carries out the transfer of the amide group of glutamine to 2‐oxoglutarate to yield two molecules of glutamate and thus completes the assimilation of ammonia into amino acids. This GS/GOGAT pathway of ammonia assimilation is of crucial importance for crop growth and productivity and ultimately animal and human nutrition. Glutamate dehydrogenase (GDH) is now considered to be only involved in glutamate catabolism to form ammonia, an important role in N recycling within the plant. Nitrogen is also often diverted from glutamine to asparagine as a temporary measure during periods of carbohydrate shortage and excess of reduced nitrogen. This diversion requires the action of asparagine synthetase in the anabolic reaction and asparaginase in the catabolic reaction. This chapter describes the properties of these enzymes in the assimilation and reassimilation of nitrogen and in particular the genes that encode them, their complexity and the time and place they are expressed. Plant transformation has allowed the construction of a range of plants with enhanced and decreased activity of several of these enzymes, some of which have shown improved agronomic performance.