On the basis of a comparison of theoretical quantum calculations, by both semiempirical and ab initio methods, with photoemission and inverse photoemission results, we suggest that polymethylvinylidenecyanide (PMVC) adopts an all-trans conformation with few, if any, alternating trans-gauche carbon-carbon bond arrangements. The comparison of theory with the available photoemission and inverse photoemission excludes the presence of a significant fraction of gauche bonds in the polymer chains, indicative of the all-trans conformation, with dipoles all aligned.