Spectral features and photochemical reactivities were studied on poly(vinyl alcohol) bearing p-phenylenediacrylate groups (PVA-p-PDAmC2) in comparison with ethyl hydrogen p-phenylenediacrylate (p-PDAmC2). PVA-p-PDAmC2 has a very high photoreactivity compared with p-PDAmC2; this can be ascribed to the formation of ground state pairs of p-PDAmC2 moieties as side chains due to repulsive interaction between the hydrophobic side chains and the hydrophilic main PVA polymer chain. Some polymers showed features of photoresist with a resolution of 2.5 mu m.