Nanoheterostructures based on titanium dioxide synthesized by the Sol-gel method were studied. Microscopy, x-ray diffraction, optical spectroscopy, and electron paramagnetic resonance (EPR) techniques were used) All the samples under the study are characterized by a large specific surface area (about 100 square meters per gram of substance). It is established that the main types of radicals in the obtained structures are N•, Ti3+, Mo5+, V4+, and W5+, depending on the composition of the samples. It is shown that nanoheterostructures consisting of several metal oxides have high photocatalytic activity in the visible range of the spectrum and the ability to accumulate photogenerated charge carriers. As a result, the catalytic reactions in the samples continue even after the lighting is turned off. A correlation was found between the rate of photocatalysis, the absorption spectra in the visible region, and the concentration of radicals in the studied structures. The results obtained can be used to develop energy-efficient catalytic devices based on nanoheterostructures consisting of titanium, molybdenum, tungsten, and vanadium nanoxides in various combinations that operate under periodic illumination in the visible range of the spectrum. The research was carried out with the financial support of the Russian Foundation for basic research in the framework of research project No. 18-29-23051.