The effects of the molecular weight of poly(D-lactic acid) (PDLA), which forms stereocomplex (SC) crystallites with poly(L-lactic acid) (PLLA), and those of processing temperature Tp on the acceleration (or nucleation) of PLLA homocrystallization were investigated using PLLA films containing 10 wt% PDLA with number-average molecular weight (Mn) values of 5.47 × 105, 9.67 × 104 and 3.67 × 104 g mol–1 (PDLA-H, PDLA-M and PDLA-L, respectively). For the PLLA/PDLA-H and PLLA/PDLA-M films, the SC crystallites that were ‘non’-melted and those that were ‘completely’ melted at Tp values just above their endset melting temperature and recrystallized during cooling were found to act as effective accelerating (or nucleation) agents for PLLA homocrystallization. In contrast, SC crystallites formed from PDLA-L, having the lowest Mn, were effective accelerating agents without any restrictions on Tp. In this case, the accelerating effects can be attributed to the plasticizer effect of PDLA-L with the lowest Mn. The accelerating effects of SC crystallites in the PLLA/PDLA-H and PLLA/PDLA-M films was dependent on crystalline thickness for Tp values below the melting peak temperature of SC crystallites, whereas for Tp values above the melting peak temperature the accelerating effects are suggested to be affected by the interaction between the SC crystalline regions and PLLA amorphous regions.