Poly(phenylene vinylene)s (PPVs) are well known for their applications in electro-optical and photonic devices. An efficient ADMET reaction using a 4th generation Ru-based initiator (Grubbs-Hoveyda 2nd generation) afforded dimeric and trimeric units with high yields, starting from 1,4-dimethoxy-2,5-divinylbenzene. Both NMR and FT-IR showed that products have all trans-configuration at the vinylene bonds. The short methoxy side group caused pronounced differences in solublities, especially for oligomers larger than the trimer, allowing for high yields in trimer and dimer, which then could easily be isolated and purified. Both dimer and trimer have vinyl end functional groups, which can further be modified for future applications.