The notable impact of a trace amount of hydrogen peroxide (H2O2) on the photocatalytic performance of Ti-based metal–organic frameworks (MOFs), namely MIL-125 and NH2-MIL-125, in the purification of water polluted with chemical agents was studied experimentally. MIL-125 and NH2-MIL-125 were synthesized using the solvothermal method and were characterized by a variety of diagnostic methods. NH2-MIL-125 exhibited a bandgap of 2.8 eV compared to 3.65 eV for MIL-125 with optimal visible light capture capability, indicating the outstanding photodegradation activity of the synthesized MOFs. In addition, the photocatalytic performance of MIL-125 and NH2-MIL-125 was tested for the degradation of methylene blue (MB) as a chemical pollutant in water under both dark conditions and irradiation by visible light and a UVC lamp. NH2-MIL-125 exhibited a significantly higher photodegradation rate compared to MIL-125 due to the presence of the amino group, higher surface electronegativity and slightly lower bandgap. Furthermore, the effect of H2O2 as an electron acceptor on the efficiency of MB degradation was investigated, which markedly enhanced the photocatalytic MB degradation performance due to the ligand-to-metal charge transfer mechanism, particularly for NH2-MIL-125, under all tested conditions.@en