We report the development of sol–gel derived TiO₂ thin films with adjustable and defined properties suitable for memristive cell fabrication. Memristive cells were developed by the sol–gel deposition of titania onto SiO₂/Ti/Pt engineered electrodes via spin coating, followed by diverse curing and annealing procedures. The influence of the processing conditions and the sol's chemical composition on the film properties, and therefore on the memristive response, was studied by micro-Raman and transmission spectroscopies, profilometry, ellipsometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and X-ray absorption and diffraction spectroscopies (XAS and XRD). A memristive response was acquired from a number of these cells, revealing a dependence of the electrical behavior on minor changes in the TiO₂ structure, electroforming parameters, and architecture. Thus, these properties provide a handle for fine-tuning electrical performance.