Poly(p-phenylenevinylene) (PPV) films with good optical and electrical properties are desirable for optoelectronic applications. The standard synthesis involves thermal elimination from a non-conjugated precursor. Although conversion at low temperatures would be preferable in terms of improved quantum efficiency and ease of device fabrication, relatively high temperatures are needed for full PPV conversion. Here a route is presented in which rapid elimination takes place at low temperature to yield thermally stable PPV films with a high degree of conjugation and improved photoluminescence properties.