This paper proposes a method of fabricating low-dimensional TiO2 nanofilms at room temperature under ambient pressure conditions. The titanium-containing polymer complex Tip(DDA/acac) was synthesized by reacting an amphiphilic copolymer (p(DDA/acac)) with a titanium complex. Its ultrathin films were prepared using the LangmuirBlodgett (LB) technique. The monolayer was found to be free from hydrolysis and cross-linking side reactions, even at the airwater interface. The transferred LB films (nanosheets) were oxidized by ultraviolet irradiation at room temperature. The photo-oxidized material has an amorphous and porous structure with subnanometer-scale controllability (0.18 nm per layer). Photocatalytic performance was demonstrated by converting multilayered LB films of Ti(DDA/acac) and the silicon-containing polymer p(DDA/SQ) into ultrathin hetero-multilayers of TiO2 and SiO2 under UVO3 treatment. The scalability affords a uniform photopattern formation of photo-oxidized TiO2 films over several hundreds of micrometers.