Since most polymers are not inherently stable to light, their photochemical behavior remains a subject of constant interest. In this study, we investigated the photoaging behavior of polymeric colloidal photonic crystal films. As a consequence of photochemical reactions containing chain-scission, photoaging induced morphological changes in the film surface including changes in the size, surface roughness, shape, and packing structure of PS particles. These structural modifications came about the deterioration of optical properties (photonic bandgap) during photoaging. Based on our results and observations, a plausible correlation between the evolutions of the optical properties and the structural modifications during photoaging was established. Finally, the compositional modifications of the surface based on oxygen incorporation behavior caused by the photooxidation process are discussed based on the ATR-FTIR and XPS analyses. (C) 2012 Elsevier Inc. All rights reserved.