Polyvinyl chloride (PVC)/styrene‐butadiene rubber (SBR) antistatic membranes were prepared by two types of grafting, namely, self‐ and chemical grafting processes, using solvent‐casting technique via tetrahydrofuran and toluene as solvents for PVC and SBR, respectively. The membrane modification was carried out by doping orthophosphoric acid (OPA) in the polymer solution. The effect of OPA on the properties of the PVC/SBR membranes was studied in detail with respect to the electrical properties of the antistatic membranes. The electrical conductivities were improved by increasing the OPA content onto membranes. These results suggest that PVC/SBR antistatic membranes doped with OPA can be utilized as promising antistatic material candidates for fabrication of automobile tires and electronic materials.