Bis-anthracenyl and bis-thienyl polyenes have been synthesized using Wittig methodology. These polyenes can be oxidatively doped with SbCl5 to yield bipolaron-like charge states that can be cast as thin film composites. X((3)) measurements performed by degenerate four wave mixing on neutral and doped polyenes indicate significant enhancement of X((3)) by bipolaron charge state generation. In the bis-thienyl polyene series, dramatic increases in solubility and processibility have been achieved by multiple alkyl group substitution thus allowing synthesis and characterization of long polyene sequences as oligomeric models of polyacetylene.