Electrophoretic deposition (EPD) using polydimethylsiloxane (PDMS)-based organic-inorganic hybridmaterials can prepare alumina coatings on metal substrates. In this article, we investigated the influence of deposition conditions on the EPD behavior and structure of the EPD coating. We found that the PDMS-based hybrid sol and the alumina particles have different EPD behavior in the EPD suspension. It was also observed that the composition and porosity of the EPD coating can be controlled by adjusting the deposition voltage and utilizing the differences in electrophoretic behavior of alumina particles and PDMS-based hybrid sol, and by using alumina particles of appropriate morphology.