Mesoporous silica films fabricated on a conductive substrate are employed as templates for the electrochemical deposition of nanosized zinc oxide (ZnO). The ZnO-deposited mesoporous silica (ZnO-MPS) films are characterized and proved to retain the three-dimensional (3-D) cubic structure even after the electrodeposition process. Photoluminescence (PL) spectrum of ZnO-MPS film shows three main emission peaks at 451.5, 415 and 369 nm at room temperature. The emission peak at 369 nm presents apparent blue-shift than that of bulk ZnO at 384 nm, and the corresponding band-gap energy of nanosized ZnO significantly increases compared with that of bulk ZnO. These results demonstrate that the MPS films act as important templates for the electrochemical preparation of nanostructured ZnO. They also suggest the potential utility of ZnO-MPS films as optical nanodevices.