The present work investigates the intrinsic photosensitivity of a family of poly(alkyl)(aryl)silanes and poly(hydridophenyl)silane for use in the development of photoimprinted waveguide devices. Limited testing of passive optical behavior (e.g. absorption, refractive index) and photosensitive response was performed for these materials in thin film form. It was determined that the materials exhibited dramatic photobleaching under 248 nm (KrF excimer laser) exposure. Based on a Kramers-Kronig analysis of the absorption changes, refractive index changes on the order of - 0.1 are estimated. Confirmation of this calculation has been provided via ellipsometry which estimates refractive index changes at 632 nm of -0.14 ± 0.01. In addition, embedded strips have been photoimprinted into the material to confirm waveguiding capacity of the films. Possible sources of photosensitivity in this material and its potential for application in various device configurations will be discussed.