Poly(lactide)s(PLA) is an attractive material to solve the problem of waste plastic accumulation in nature because of its biodegradability. The lactide exists in three stereoisomeric configurations: L-lactide, D-lactide, and meso-lactide. PLA stereocomplexes, formed by the mixing of two enantiomers, poly(L-lactide)(PLLA) and poly(D-lactide)(PDLA), have many favorable characteristics because the stereocomplex showed $50^{circ}C$ higher melting point than each enantiomeric polymer and the resistance toward degradation increased. In this study, we investigated the influence of the composition and the optical purity of each component on the formation of stereocomplexes. Also, the nanofibers of stereochemical PLA and their blends were prepared by electrospinning method. The properties of the obtained fibers were analyzed by differential scanning calorimetry and scanning electron microscopy. The results showed that a degree of stereocomplex was controlled by change of optical purity of each component. The enzymatic degradation of the fibers were strongly dependent on the stereocomplex.