1,4-linked, stereoregular precursors to poly(p-phenylene) (PPP) are synthesized by transition-metal-catalyzed polymerization of heteroatom-functionalized 1,3-cyclohexadienes. cis-5,6-Bis(trimethylsiloxy)-1,3-cyclohexadiene (TMS-CHD), a derivative of a microbial oxidation product of benzene, is polymerized stereospecifically in a cis-1,4-fashion by bis[(eta(3)-allyl)(trifluoroacetato)nickel(II)] with yields up to 96%. This polymerization system not only affords a highly 1,4-linked, stereoregular polymer but also permits a degree of molecular weight control. The resulting polymer, 1,4-poly(TMS-CHD), is a soluble, processable, semicrystalline material. Although 1,4-poly(TMS-CHD) cannot be pyrolyzed to yield PPP directly, the trimethylsilyl ethers on the polymer can be easily transformed to better leaving groups such as acetates to give the corresponding stereoregular acetoxy polymer (100% acetylation; 93% overall yield). NMR analysis of the acetoxy polymer is consistent with the polymer having either a highly isotactic or a highly syndiotactic cis-1,4-linked structure.