Abstract This article describes a study of the influence of parameters of the hydrothermal synthesis on the structural characteristics and photocatalytic activity of the materials synthesized from peroxytitanium complex precursor. The materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning and transmission electron microscopy (SEM and TEM). The active oxidative species produced on the photocatalyst surface were investigated by measuring the fluorescence derived from their reaction with terephthalic acid (TPA). Also, the photocatalytic efficiency of the synthesized materials was assessed by monitoring the degradation of the methylene blue (MB) dye. The morphological characteristics and photocatalytic efficiency of the synthesized materials exhibited greater dependence on temperature than time of synthesis. The photocatalytic results show that the main factor for the effectiveness of the synthesized materials was crystallinity. Furthermore, it was observed that the photodegradation process occurred by the attack of active radicals on the MB molecules and not by the direct oxidation of adsorbed MB molecules on the photocatalyst surface.