The structural and synthetic aspects related to α-oxyiminophosphorus derivatives are reviewed. This includes their preparation through reactions involving C-N double bond or P-C single bond formation as well as the O-functionalization or transformations at the phosphorus atom of other phosphorus substituted oximes. Moreover the synthetic features of α-oxyiminophosphorus derivatives include the reduction of the oximo group with selective preparation of biologically active α-amino-phosphonate and -phosphinate derivatives, as well as the oxidative transformations on the oxime group, rearrangement versus fragmentation reactions, radical reactions and formation of metal complexes