A visible-light photocatalytic performance of 3-aminopropyltriethoxysilane (APTES)-modified TiO2 nanomaterials obtained by solvothermal modification under elevated pressure, followed by calcination in an argon atmosphere at 800–1000 °C, is presented for the first time. The presence of silicon and carbon in the APTES/TiO2 photocatalysts contributed to the effective delay of the anatase-to-rutile phase transformation and the growth of the crystallites size of both polymorphous forms of TiO2 during heating. Thus, the calcined APTES-modified TiO2 exhibited higher pore volume and specific surface area compared with the reference materials. The change of TiO2 surface charge from positive to negative after the heat treatment increased the adsorption of the methylene blue compound. Consequently, due to the blocking of active sites on the TiO2 surface, the adsorption process negatively affected the photocatalytic properties. All calcined photocatalysts obtained after modification via APTES showed a higher dye decomposition degree than the reference samples. For all 3 modifier concentrations tested, the best photoactivity was noted for nanomaterials calcined at 900 °C due to a higher specific surface area than materials calcined at 1000 °C, and a larger number of active sites available on the TiO2 surface compared with samples annealed at 800 °C. It was found that the optimum concentration for TiO2 modification, at which the highest dye decomposition degree was noted, was 500 mM.