The synthesis and characterization of two new soluble poly(p-phenylenevinylenes) (PPVs) are reported. The polymers are poly(2-2',5'-bis(octyloxy)benzene)-1,4-phenylenevinylene) (BOP-PPV) and poly(2-(2',5'-bis(octyloxy)benzene)-5-methoxy-1,4-phenylenevinylene) (BOPM-PPV). Both polymers have been polymerized at high and low temperatures to study the formation of structural defects. It is shown that both methoxy groups as side chains and low polymerization temperatures decrease the content of defects in the final polymer. As a consequence, the polymers with lower concentration of defects exhibit higher electroluminescence yields in light-emitting diodes. In addition to this, the polymers with a low content of defects exhibited longer operational lifetimes in these devices. The highest photoluminescence quantum yield in the solid state and electroluminescence efficiency were found to be 72% and 1.74%, respectively.