Chlorinated polyethylene (CPE) prepared by solid-state chlorination was used as a compatibilizer for poly(vinyl chloride) (PVC)/linear low-density polyethylene (LLDPE) blends. Effects of CPE molecular structure on stress-strain behaviors, dynamic mechanical properties, and morphologies of PVC/LLDPE blends were studied by using SEM, TEM, DMA, and testing mechanical properties. The results showed that the compatibility of PVC/LLDPE blends was improved with the addition of CPE. Also, adhesion strength between the two phases and mechanical properties of the blends were increased.