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[Display omitted] • E–TiO 2 @rGO with OVs were prepared through crystal defect engineering. • Mixed crystal and OVs enhanced electron-hole pairs separation efficiency. • E–TiO 2 @rGO improved 2,4,6-TCP dichlorination process and degradation efficiency. • The toxicity of 2,4,6-TCP and its intermediates was evaluated via ECOSAR and DFT. Chlorophenolic pollutants pose serious threats to the aquatic ecosystem. Photocatalysis technology has broad prospects for decontamination. In this work, MXene-derived TiO 2 nanocomposites with mixed-crystal characteristics and oxygen vacancies (OVs) (E–TiO 2 @rGO) were successfully synthesized by atmosphere modulation. Compared with commercial TiO 2 and N 2 –TiO 2 @rGO (anatase phase), the rate constants of E–TiO 2 @rGO (0.06874 min−1) over 2,4,6-trichlorophenol (2,4,6-TCP) degradation increased 4 and 1.3 times, respectively. The enhanced photocatalytic performance was attributed to the co-existence of anatase and rutile phases. On the one hand, the mixed-crystal phase narrowed the band gap, broadening the light absorption range. On the other hand, it induced the generation of OVs, which has been demonstrated by DFT calculation. The presence of OVs improved the adsorption and activation of O 2 and H 2 O molecules, beneficial for the formation of active free radicals. In addition, the incorporation of rGO promoted the separation of electron-hole pairs. The Gibbs free energy of 2,4,6-TCP degradation revealed that the OVs and mixed-crystal could reduce the energy barrier of the rate-determining step, thereby boosting the dichlorination efficiency of 2,4,6-TCP. The superoxide free radical (O 2 −) was determined as the dominant active species. Finally, a possible mechanism of 2,4,6-TCP degradation with E–TiO 2 @rGO was clarified clearly. The proposed mixed-crystal defect engineering represents a novel strategy in the design and synthesis of photocatalysts. [ABSTRACT FROM AUTHOR]