Block-copolymer containing a poly(L-lactic acid) (PLLA) segment was blended with pure poly(D-lactic acid) (PDLA) chain in chloroform solution and casted into the dried film. This method could form the stereocomplex (Sc) crystal of PLLA/PDLA within the nanometer-sized phase separation self-assembled by block-copolymer. Differential scanning calorimetry measurements of the prepared and annealed films gave the maximum achievable melting temperature of 245 °C, which was highest among those previously reported for PLA Sc-crystals. Surprisingly, all of added PDLA chains were Sc-crystallized, depending on the blend composition with block-copolymer containing PLLA.