Titanium dioxide was synthesized via hydrolysis of titanium (IV) isopropoxide using a sol–gel method, under neutral or basic conditions, and heated in the microwave-assisted solvothermal reactor and/or high-temperature furnace. The phase composition of the prepared samples was determined using the X-ray diffraction method. The specific surface area and pore volumes were determined through low-temperature nitrogen adsorption/desorption studies. The photoactivity of the samples was tested through photocatalytic reduction of carbon dioxide. The composition of the gas phase was analyzed using gas chromatography, and hydrogen, carbon oxide, and methane were identified. The influence of pH and heat treatment on the physicochemical properties of titania-based materials during photoreduction of carbon dioxide have been studied. It was found that the photocatalysts prepared in neutral environment were shown to result in a higher content of hydrogen, carbon monoxide, and methane in the gas phase compared to photocatalysts obtained under basic conditions. The highest amounts of hydrogen were detected in the processes using photocatalysts heated in the microwave reactor, and double-heated photocatalysts.