In this work, a one-pot hydrothermal route was synergistically applied for TiO2 immobilized reduced graphene oxide (TiO2/rGO) facilitation. The material was characterized by modern analysis methods and studied the photocatalytic performance with methylene blue (MB) in the water. The characteristic results expressed that TiO2 in truncated octahedral bipyramidal structure with 4–25 nm was disseminated onto the rGO base. Simultaneous effects of the reaction temperature, pH, adsorption time, photocatalytic time, MB concentration, and catalyst dosage on the MB photodegradation of TiO2/rGO were also conducted by full factorial experimental design according to Placket–Burman and Box–Behnken designs. At room temperature, after 2h–adsorption and photodegradation with MB concentration of 23 mg/L in pH of 10 solution and 20 mg catalyst, nearly 100% of MB was productively decomposed out of the medium with a relatively high reaction rate constant. The photocatalytic performance showed an excellent impact toward other types of organic contaminants with the above condition, indeed affirming an extensive use in wastewater treatment with organic pollutants.