Catalytic asymmetric reactions provide one of the most powerful and economical synthetic approaches to a variety of enantiomerically enriched compounds. As being analogues of the corresponding α- and β-amino acids, optically active α- and β-amino phosphonic acid derivatives have found widespread use in medicinal chemistry and the pharmaceutical sciences. Using catalytic amounts of chiral materials, asymmetric synthesis of enantiomerically enriched α- and β-amino phosphonates has been a subject of growing interest. This tutorial review contains a compilation of the catalytic asymmetric synthetic methods developed to date and highlights their utility for obtaining these target compounds.