l-Lactide-rich poly(l-lactide) (LR-PLLA)/d-lactide-rich poly(d-lactide) (DR-PDLA) blends with moderate optical purity were prepared by conventional extrusion and followed by injection-molding process in this study. Thermal properties, crystalline structure, spherulite morphology, melt degradability, and thermal mechanical property were investigated by means of DSC, WAXD, POM, TG, and DMA. In comparison with LR-PLLA/DR-PDLA blends with higher optical purity, stereocomplex with less perfect structure was partially formed from the LR-PLLA/DR-PDLA blends with various compositions and showed lower melting temperature. Surprisingly, double melting peaks have appeared in blends with 40 or 50 wt% DR-PDLA. Annealing at higher temperature for blends with 50 wt% DR-PDLA resulted in three melting peaks. It is assumed that the optical purity would play a critical role, thus, producing limited amount of stereocomplex with less imperfect structure. Annealing would also induce the micro-phase separation behavior in LR-PLLA/DR-PDLA blends and significantly influence the thermal and degradable properties of blends.