TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO2@C, and that microwave irradiation can be advantageous for the synthesis of carbon-based materials. Composites of TiO2 with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO2 nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO2 is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance. Microwave heating promotes the covalent attachment of titanium dioxide particles to carbon nanomaterials. This method is more effective than conventional methods. The structures with the stabilized oxide show improved photocatalytic properties.