In order to improve toughness of rigid poly(vinyl chloride) (PVC), we prepared multilayer graphene (MLG) filled PVC composites through conventional melt‐mixing methods by taking advantages of easy dispersion and high flexibility of graphene. Microstructure, static, and dynamic mechanical properties of the MLG/PVC composites were investigated in details. We found that a small amount of MLG loadings (0.36 wt%) could greatly increase tensile fracture toughness and impact strength of the MLG/PVC composites, which is mainly attributed to high flexibility of the crumpled MLG throughout PVC matrix. Moreover, the presence of MLG can weaken intermolecular interactions and improve segmental motion of PVC chains, consequently resulting in low glass transition temperature and high toughness of the MLG/PVC composites. By virtue of its enhanced toughness and easy operation, the MLG/PVC composites show great potential to be used as high‐performance composites in many fields.