Abstract Highly functionalized reduced graphene oxide (rGO) sheets, decorated with homogenously distributed titanium dioxide (TiO 2 ) nanoparticles, were obtained by optimizing the conditions of a facile solvothermal synthesis route with methanol‐water as solvent. These materials show a Raman enhancement apparently at the rGO/TiO 2 interface. Conventional and High Resolution Transmission Electron microscopy (HRTEM) and X‐ray diffraction (XRD) show single crystal TiO 2 NPs below 6 nm with an anatase crystalline phase. Fourier Transform Infrared (FT‐IR) spectroscopy shows a significant chemical reduction of the graphene oxide. Thermal analysis also confirms the efficient functionalization and in‐situ reduction of the graphene oxide sheets. The results show that under mild conditions, the solvent mixture achieves a higher functionalization than pure solvents.