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The release of phenolic-contaminated treated palm oil mill effluent (TPOME) poses a severe threat to human and environmental health. In this work, manganese-modified black TiO₂ (Mn-B-TiO₂) was produced for the photodegradation of high concentrations of total phenolic compounds from TPOME. A modified glycerol-assisted technique was used to synthesize visible-light-sensitive black TiO₂ nanoparticles (NPs), which were then calcined at 300 °C for 60 min for conversion to anatase crystalline phase. The black TiO₂ was further modified with manganese by utilizing a wet impregnation technique. Visible light absorption, charge carrier separation, and electron–hole pair recombination suppression were all improved when the band structure of TiO₂ was tuned by producing Ti³⁺ defect states. As a result of the enhanced optical and electrical characteristics of black TiO₂ NPs, phenolic compounds were removed from TPOME at a rate of 48.17%, which is 2.6 times higher than P25 (18%). When Mn was added to black TiO₂ NPs, the Ti ion in the TiO₂ lattice was replaced by Mn, causing a large redshift of the optical absorption edges and enhanced photodegradation of phenolic compounds from TPOME. The photodegradation efficiency of phenolic compounds by Mn-B-TiO₂ improved to 60.12% from 48.17% at 0.3 wt% Mn doping concentration. The removal efficiency of phenolic compounds from TPOME diminished when Mn doping exceeded the optimum threshold (0.3 wt%). According to the findings, Mn-modified black TiO₂ NPs are the most effective, as they combine the advantages of both black TiO₂ and Mn doping.