We demonstrate that a photochemical reaction can create various distributions of refractive index in polymer. When the polymer containing a photochemically active material is irradiated by UV light, the photochemical reaction which breaks the-conjugated system in the material and decreases its linear polarizability can reduce refractive index of the polymer. We prepared a PMMA film added DMAPN ͑͑4-N,N-dimethylaminophenyl͒-NЈ-phenylnitrone͒ with a rate of 23 wt % by use of spin coating. Electronic structural change of DMAPN and refractive indices of the film before and after UV irradiation were evaluated by UV absorption spectra and m-line method, respectively. The UV irradiation decreased max at 380 nm in the absorption spectra, which is attributed to nitrone, and the refractive indices exponentially with irradiation time. The change of refractive indices reached 0.028. The refractive index profile upon depth of the film was investigated by measuring refractive indices of stacked DMAPN/PMMA films. When UV with a power of 10.7 mW/cm 2 irradiated upon three stacked DMAPN/PMMA films for 35 s, variation of the refractive index change showed a quadratic profile. The refractive index profile with various irradiation time can be accounted with the combination of the chemical kinetics with the steady state approximation and Lambert-Beer's law. Thus, the photochemical reaction can be used to control the refractive index distribution in polymer.