We present the synthesis and characterization of poly(2-(2",5'-bis(2"-ethylhexyloxy)phenyl)-1,4-phenylenevinylene) (BEHP-PPV) polymerized at different temperatures. The photoluminescence efficiencies in the solid state of BEHP-PPV obtained at 144 and 0 degreesC are 28% and 60%, respectively. H-1 NMR measurements showed a lower concentration of structural defects for BEHP-PPV obtained at lower temperatures, which can explain the increased photoluminescence efficiencies for these polymers. Polymerization temperatures below 0 degreesC decrease the molecular weight without changing the photoluminescence efficiency to any large extent. The electroluminescence efficiencies follow the trend in the photoluminescence efficiencies.