A photocrosslinkable polymer liquid crystal (PPLC) can be used to form aligned mesoporous silica thin films. Crosslinking the biphenyl mesogens with linearly polarized UV light results in a photo-oriented film whose orientational order is subsequently increased by annealing. Addition of a precursor sol produces high-quality silica films (see Figure) which can be used for optical devices that incorporate functional dyes or metal clusters into the channels.