A new vinylmonomer with a large pendant π-electron group was synthesized. α- Naphthylmethylvinylether and 3-pyrenylmethylvinylether were polymerized in good yields, although their polymers have fairly low molecular weights. Both polymers have a fairly high isotacticity. Poly-3-pyrenylmethylvinylether showed a large photocurrent in its absorption region and a small photocurrent even above 500 to 1000 mμ. The doped TCNE ...