A wet layer-by-layer self-assembly of composite TiO2/polymer films on Si and Al2O3/Al, substrates has been studied by AFM, STM, and ellipsometry techniques. The quality of the first adsorbed TiO2 layer has been found to be the governing factor in multilayer film growth. The first layer consists of single particles and particle agglomerates 30-120 nm wide The surface coverage in the layer is determined by the chemical composition of the substrate surface and water pH in post-adsorption rinsing procedure. Well-packed TiO2/polymer film completely covering the surface has been prepared in five adsorption cycle on Al2O3Al substrate. The film remained crack-free after heat treatment at 300 degrees C. I-V curves measurement reveals high resistivity (R similar to 10(10) O in the voltage range from -2 to +3 V) of TiO2/polymer films prepared in ten adsorption cycles.