ABSTRACTTwo functional polysilsesquioxane microspheres, poly(epoxypropoxy)silsesquioxane (PESQ) and poly(epoxypropoxy/amino)silsesquioxane (PEASQ), were grafted onto commercial polylactic acid (PLA) via functional group reactions through melt processing and directly used as novel chain extenders to improve the thermal stability of PLA. During the whole reaction time of 35 min, the torques of P‐2PESQ and P‐1PEASQ were 60% higher than that of processed PLA. Thermal gravimetric analysis (TGA) revealed that the addition of PESQ or PEASQ into PLA increased the onset temperature for thermal degradation. PEASQ was found to be a potential chain extender for PLA. Compared with the processed PLA, the thermal decomposition temperatures of PEASQ modified PLA increased from 318 to 334°C at 5% weight loss. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41977.