A new precursor route for poly(arylene vinylene) derivatives will be presented. In this way non‐ionic precursor polymers are obtained which show an enhanced thermal stability and are soluble in organic solvents. This enables a thorough structural characterization and the study of the mechanism. Experiments have been performed to differentiate between a radical or an ionic polymerization mechanism. Furthermore possibilities to tune solubility characteristics and to introduce defects in the polymer backbone will be discussed. Also the scope for this new route was explored. The first results indicate that the versatility exceeds that of the Wessling route, e.g. the synthesis of precursors for poly(p‐biphenylene vinylene) and poly(2,6‐naphthylene vinylene) could be accomplished in our case, whereas it failed in the case of the Wessling route.