Patterned thin films of TiO2were deposited from aqueous solution onto photopatterned self‐assembled monolayer (SAM) films on Si substrates. Regions of the SAM containing sulfonate surface functionality were created by the photo‐oxidation of initially deposited thioacetate groups through a mask. The nanocrystalline TiO2‐on‐SAM films were deposited selectively on the photolyzed regions of the SAM. The electrical properties of such films were assessed for potential microelectronic device applications. Current–voltage and capacitance–voltage measurements made on nonpatterned TiO2films yielded values of relative permittivity ranging from 24 to 57, film resistivities of 1.0–1.5×109&OHgr; cm and breakdown voltages in excess of 1 MV/cm. ©1996 American Institute of Physics.