The capability of ammonium 18-molybdodiphosphate, (NH4)(6)P2Mo18O62 (Mo-18(6-)), and ammonium 18-tungstodiphosphate, (NH4)(6)P2W18O62 (W-18(6-)), to photochemically generate acid within films of a polymer with hydroxylic functional groups (namely, within poly(2-hydroxyethyl methacrylate) (PHEMA) films) is demonstrated. Upon UV irradiation, both 2:18 polyoxometalates (POMs) investigated are reduced with concomitant oxidation of PHEMA and generation of acid, which subsequently catalyzes the cross-linking of PHEMA. The photoacid generation is mainly evidenced by monitoring the protonation of an appropriate acid indicator (4-dimethylamino-4'-nitrostilbene) with UV spectroscopy and by photolithographic imaging experiments. By comparing the efficiency of both POMs to induce acid-catalyzed cross-linking of PHEMA under similar conditions, the W-18(6-) ion is found to be more efficient in photoacid generation than the Mo-18(6-) ion. Imaging of the POM-containing PHEMA films through UV photolithographic processing is demonstrated. In that process, both POMs can be entirely leached during the development step by using pure water as a developer, resulting in patterned PHEMA films. This characteristic renders the investigated POMs attractive materials for applications, especially in the area of biomaterials, where removal of the photoacid generator from the film at the end of the process is desirable.