Precise deconvolution of grain and grain boundary contributions to the overall impedance of TiO2 thin films is achieved by impedance spectroscopy measurements of textured films with elongated grains obtained by laser-induced melting and sequential lateral solidification. The ability to engineer the grain morphology of electroceramic films provides opportunities for new designs of ferroelectric memories, piezoelectric microsensors and microactuators, optical waveguides, and other devices.