Abstract The polymerization of p-chloromethyl styrene was conducted by using metallic cationic initiators generated electrochemically. The molecular weight of the polymer obtained by using V, Ti, Cr, Al and Hg was in the range 1000–4000. The effect of type of metallic initiator and the anion of the supporting electrolyte on the yield and degree of polymerization was investigated. All the tested metals gave polymerization with good yields. The better yields and higher degrees of polymerization were achieved with Hg and A1 metals and in presence of (SbF 6) − and (ClO 4) − as anions of supporting electrolytes due to the stability and poor nucleophilicity of these anions. The polymer obtained was identified by carrying out FT-IR and 1H-NMR spectral analysis.