We present experimental results of photochromic reactions induced by single- and two-photon excitations in a poly(methyl methacrylate) thin film doped with spirobenzopyran. We also demonstrate the operation of a spirobenzopyran-doped poly(methyl methacrylate) planar waveguide, prepared by cast spinning the media onto fused-quartz slides. The following phenomena were shown to take place in this waveguide: single-twophoton coloring, f luorescing, and bleaching. The results indicate that such devices may be suitable for many applications, including optical waveguides, volume optical storage, and optical sensors.