We provide an overview of the current progress in the synthesis of poly(p-phenylene vinylene) (PPV) polymers. The described synthetic approaches can be divided into four main categories: polymerization of quinodimethane intermediates, metathesis polymerization, nucleophilic polycondensation, and palladium-catalyzed cross-coupling. While such variety is remarkable and very high-molecular-weight PPV can be prepared by some methods, the synthetic chemistry of PPV still limits the structural variety and purity of arylene vinylene polymers. In particular, palladium-catalyzed cross-coupling reactions, the method of choice in the contemporary conjugated polymer chemistry, often shows limited success in PPV series. On the other hand, the possibility of using metathesis polymerization creates new opportunities not available for other classes of conjugated polymers.