Synthesis and characterization of poly(quinoxaline vinylene)s and poly(pyridopyrazine vinylene)s with linear and branched aliphatic side chains are reported. The electron affinity of the polymers was measured with cyclic voltammetry (CV) and found to be highest for the pyridopyrazine vinylene polymers, Compared to CN-MEH-PPV, the pyridopyrazine vinylene polymers were easier to reduce, while the quinoxaline derivatives were harder. UV-vis absorption measurements showed that the polymers have relatively small band gaps.