Pyrrolidines, the 5 membered aza-heterocycles, substituted at the 2 and 5 positions, are very often encountered in the living organisms, and possess interesting biological properties. It is worthy of note that besides the potential use of these compounds as chemotherapeutic agents, the 2,5-disubstituted pyrrolidines possessing a C2 symmetry axis may be used as very powerful catalysts in numerous asymmetric reactions. This review will focus on the stereoselective syntheses of 2,5-disubstituted pyrrolidines and will be subdivided in two main sections: (1) where the 5 membered ring is formed by a stereospecific method and (2) where the already formed ring is functionalized at the 2 and 5 positions.