The synthesis and characterization of two soluble poly(p-phenylenevinylene)s substituted with phenyl groups on the vinylene moiety is reported. The polymers are poly(1,4-phenylene-1,2-diphenylvinylene) (PPV-DP) and poly(1,4-phenylene-1,2-(3'-(2?-ethylhexyloxy))-diphenylvinylene) (PPV-mEHDP). The monomers containing chloromethyl groups were polymerized with excess potassium tert-butoxide in dioxane at room temperature. The polymerization conditions are optimized. The photoluminescence (PL) properties of the polymers showed an increase in the PL efficiency in film from 19% for PPV-DP to 37% for PPV-mEHDP. Both polymers emitted green light with higher intensity in film than in solution.