α,β-Diamino acids have attracted considerable attention recently due to their growing importance in pharmaceutical and biochemical research. For example, this special class of diamino acids has become the components of enzyme inhibitors, and has been incorporated into peptides which are used to modulate secondary and tertiary structural conformations. Although their widely occurrence in nature, optically active α,β-diamino acids are hard to isolate and purify from available natural resources on large scale. Therefore, their asymmetric synthesis becomes a great interest for organic and medicinal chemists. However, there still exist great challenges for enantioselective synthesis of α,β-diamino acids, especially those with two vicinal chiral centers. This review highlights the recent promising methodologies for enantioselective synthesis of α,β-diamino acids, with special emphasis on catalytic asymmetric reactions, as well as methods for natural chiral compound derivatization, and chiral auxiliaries.