We report on enhancing crystallization and heat resistance of poly(l-lactic acid) (PLLA) by d-sorbitol as a small molecule nucleating agent via melt blending. During the reheating process, the cold crystallization disappeared and the crystallinity of nucleated PLLA exceeded 50%. The heat deflection temperature of PLLA was elevated from 56 to 132 °C by simply increasing the mold temperature (90 °C) without an additional annealing treatment. We also observed the polymorphic crystals of PLLA during melt crystallization, i.e., the coexistence of hexagonal and lenticular crystals, along with their various geometrical aggregates in addition to plenty of conventional spherulites. On the basis of the fact that the nonisothermal crystallization temperature of PLLA (110 °C at a cooling rate of 10 °C/min) was higher than the melting point of d-sorbitol (about 93 °C), we speculated that d-sorbitol promoted the crystallization of PLLA through a homogeneous nucleation mechanism.