Organized mesoporous TiO2 with high porosity and good interconnectivity is prepared. Low-cost amphiphilic PVA–PMMA comb copolymer was used as template. Selective interactions of Ti precursor with the PVA main chains were confirmed. Organized mesoporous TiO2 enhanced the light penetration and interfacial adhesion. Polymer electrolyte DSSC based on PVA–PMMA showed an improved efficiency.