Nano-SiO2 was modified using silane coupling agent (KH-550) and hyperbranched poly(amine-ester) respectively, and Poly(vinyl chloride) (PVC)/modified nano-SiO2 composites were made by melt-blending. The composites’ structures andmechanical properties were characterized by transmission electron microscopy(TEM), sanning electronic microscopy(SEM) and electronic universal testing machine. The results show that nano-SiO2 grafted by hyperbranched poly (amine-ester) increases obviously in dispersion in PVC matrix, and mechanical properties of PVC are effectively improved. Moreover, it was found that mechanical properties of PVC/nano-SiO2 composites reach the best when weight percent of nano-SiO2 in PVC matrix is 1%. Compared with crude PVC, the tensile strength of hyperbranched poly (amine-ester) grafted nano-SiO2/PVC composite increases by 24.68% and its break elongation, flexural strength and impact strength increase by 15.73%, 4.07% and 1841.84%, respectively. Moreover, the processing of the composites is improved.