We have found that by the inclusion of a conjugated spacer it is possible to synthesise a poly(1,4-phenylenevinylene) derivative with an electron-withdrawing group attached directly from the substituted monomer. We describe a route for the synthesis of an electronically asymmetric styryl-derivatised poly(1,4-phenylenevinylene). The preparation was achieved in two steps from the nitrostyryl-substituted arylenedimethylene bisbromo monomer 13. In the first step, base-induced polymerisation of 13 afforded the soluble and processible precursor polymer 14. The precursor polymer 14 could then be converted in the second step to the insoluble and unprocessible conjugated polymer 15 by thermal treatment in the solid state.