A new poly(phenylenevinylene) [PPV] derivative 8 with dialkoxy substituents at the 2,3- positions of the phenylene ring of the polymer backbone has been prepared. This exhibited significantly different properties compared with the typical 2,5-dialkoxy substituted PPV derivatives. The polymer is not only significantly blue-shifted in its optical and luminescence properties but also has high photoluminescence (PL) and electroluminescence (EL) efficiencies. Investigation of the model oligomer 11 offers insight into this interesting behavior.