Abstract Head-to-head poly(1-vinylnaphthalene) was synthesized by a sequence of five reactions and the polymer was characterized by its infra-red and nuclear magnetic resonance spectra. Methyl 1-naphthylacetate was brominated to methyl 2-bromo-2(1-naphthyl)acetate, which was coupled with a copper-zinc couple to dimethyl 2,3-di(1-naphthyl)succinate, a mixture of stereoisomers, which was separated into the meso and racemic compounds. Lithium aluminium hydride reduction of dimethyl 2,3-di(1-naphthyl)succinate gave 2,3-di(1-naphthyl)butanediol-1,4; the two hydroxyl groups were replaced with bromine to 2,3-di(1-naphthyl)-1,4-dibromobutane. Polymerization by Grignard coupling reaction with copper/salt catalysts gave head-to-head poly(1-vinylnaphthalene) in low yield and of relatively low molecular weight.