New dipolar and non-dipolar poly(phenylenevinylene) dendrimers bearing electron-donating and electron-withdrawing groups have been efficiently synthesized using Heck and Horner−Wadsworth−Emmons reactions. The photoluminescence of these systems may be tuned in the blue zone by choosing the appropriate peripheral groups. Despite the meta-substitution pattern, large Stokes shifts can be observed when π-donor and π-acceptor groups are connected by a m-phenylenevinylene system.