Stilbene is known to undergo two different reactions upon photochemical excitation. The first is an E/Z isomerization and the second is a [2 + 2]-cycloaddition of two stilbene molecules. Because both reactions occur in parallel their use is limited. Here we report on photorefractive polymers with a methacrylate backbone and covalently attached 4-hydroxy-(E)-stilbene or 3,5-dimethoxy-4-hydroxy-(E)-stilbene units in the side chain which show [2 + 2]-cycloaddition only. Both polymers, poly(4-methacryloyloxy-(E)-stilbene) (PMAES) and poly(4-methacryloyloxy-3,5-dimethoxy-(E)-stilbene) (PMADMES), show very high initial refractive indices of 1.6533 for PMAES and 1.6288 for PMADMES. The photochemical reaction upon laser irradiation with 355 nm was monitored by UV/vis, fluorescence, and IR spectroscopy. The light-induced changes of the refractive index at 633 nm measured by surface plasmon resonance (SPR) were found to be Delta n > 0.05 for PMAES and Delta n > 0.04 for PMADMES. The sensitivity of PMADMES is enhanced compared to PMAES due to the electron donating groups (EDG) as the direct comparison of both polymers shows. Both polymers are useful for optical devices because they do not show any absorption in the visible range and are noncrystalline as determined by wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC).