It has been more than 50 years since the first phospho-aldol reactions of dialkyl phosphites were reported. These efficient P-C bond-forming reactions have become the cornerstone of methods for the synthesis of α-hydroxyphosphonates and, by numerous available substitution reactions, the synthesis of other α- and γ-substituted phosphonates and phosphonic acids. Much of the interest in α- and γ-substituted phosphonates and phosphonic acids has been stimulated by reports of their biological activity, which is often dependent upon their absolute and relative stereochemistry. In this chapter, we review diastereoselective and enantioselective additions of dialkyl phosphites to aldehydes and ketones, otherwise called the phospho-aldol, Pudovik or Abramov reactions.