Abstract: The synergism of ethylene-propylene-diene monomer copolymer (EPDM) and dicumyl peroxide (DCP, a crosslinking agent) in low density polyethylene (LDPE)/poly(vinyl chloride) (PVC) blends was investigated. When EDPM and DCP are added to the blends simultaneously, the tensile properties could be improved significantly, especially for the blends with LDPE matrix. For example, incorporation of 10/1 (mass ratio) EPDM/DCP improves the tensile strength of the LDPE/PVC (mass ratio 80/20) blend from 7.9 MPa to 8.5 MPa and the elongation at break from 25% to 503%. Results from selective extraction, phase-contrast microscopy and thermal analysis reveal that the improvement in the tensile properties of the blends with LDPE matrix is principally due to the formation of a fine crosslinking network of the LDPE and EPDM phase. The outstanding modification effect of EPDM is explained by its dual functions: molecular entanglement with LDPE and the enhanced efficiency of DCP in the blends.