S-doped TiO₂ and hybrid MoS₂/TiO₂ systems have been synthesized, via the sulfidation with H₂S of the bare TiO₂ and of MoO supported on TiO₂ systems, with the aim of enhancing the photocatalytic properties of TiO₂ for the degradation of carbamazepine, an anticonvulsant drug, whose residues and metabolites are usually inefficiently removed in wastewater treatment plants. The focus of this study is to find a relationship between the morphology/structure/surface properties and photoactivity. The full characterization of samples reveals the strong effects of the H₂S action on the properties of TiO₂, with the formation of defects at the surface, as shown by transmission electron microscopy (TEM) and infrared spectroscopy (IR), while also the optical properties are strongly affected by the sulfidation treatment, with changes in the electronic states of TiO₂. Meanwhile, the formation of small and thin few-layer MoS₂ domains, decorating the TiO₂ surface, is evidenced by both high-resolution transmission electron microscopy (HRTEM) and UV-Vis/Raman spectroscopies, while Fourier-transform infrared (FTIR) spectra give insights into the nature of Ti and Mo surface sites. The most interesting findings of our research are the enhanced photoactivity of the MoS₂/TiO₂ hybrid photocatalyst toward the carbamazepine mineralization. Surprisingly, the formation of hazardous compounds (i.e., acridine derivatives), usually obtained from carbamazepine, is precluded when treated with MoS₂/TiO₂ systems.