Double optical monitoring is applied to determine the influence of main process parameters on the formation of sulfated zirconia and self-assembled mesoporous silica solgel films by dip coating. In addition, we analyze, for the first time to the best of our knowledge, the influence of withdrawal speed, temperature, and relative humidity on refractive-index and physical thickness variations (uncertainties of Ϯ0.005 and Ϯ7 nm) during the process. Results provide insight into controlled production of single and multilayer films from complex fluids by dip coating.