Corn starch was plasticized by glycerol suspension in a twin-screw extruder, in which the glycerol suspension was the pre-dispersion mixture of glycerol with nano-SiO2. Polylactide (PLA)/thermoplastic starch/SiO2 composites were obtained through melt-blending of PLA with thermoplastic starch/SiO2 in a twin-screw extruder. The nonisothermal crystallization behavior of PLA in the composites was investigated by differential scanning calorimetry. An interface of PLA with thermoplastic starch was proven to exist in the composites, and its interfacial bonding characteristics were analyzed. The interfacial binding energy stemming from PLA with thermoplastic starch exerts a significant influence on the segmental mobility of PLA at the interface. The segmental mobility of PLA is gradually improved by increasing interfacial binding energy, and consequently, the relative crystallinity on the interface exhibits progressive promotion. The Jeziorny model could well describe the primary crystallization of PLA in the composites. The extracted Avrami exponents based on the Jeziorny model indicate that the primary crystallization of PLA follows heterogeneous nucleation and three-dimensional growth. This study has revealed the intrinsic effect of the interfacial segmental mobility on the nonisothermal crystallization behavior of PLA in composites, which is of technological significance for its blow molding.