The Ti3C2 quantum dots (QDs)/oxygen-vacancy-rich BiOBr hollow microspheres composite photocatalyst was prepared using solvothermal synthesis and electrostatic self-assembly techniques. Together, Ti3C2QDs and oxygen vacancies (OVs) enhanced photocatalytic activity by broadening light absorption and improving charge transfer and separation processes, resulting in a significant performance boost. Meanwhile, the photocatalytic efficiency of Ti3C2 QDs/BiOBr-OVs is assessed to investigate its capability for oxygen evolution and degradation of tetracycline (TC) and Rhodamine B (RhB) under visible-light conditions. The rate of oxygen production is observed to be 5.1 times higher than that of pure BiOBr-OVs, while the photocatalytic degradation rates for TC and RhB is up to 97.27% and 99.8%, respectively. The synergistic effect between Ti3C2QDs and OVs greatly enhances charge separation, leading to remarkable photocatalytic activity. Furthermore, the hollow microsphere contributes to the enhanced photocatalytic performance by facilitating multiple light scatterings and providing ample surface-active sites. The resultant Ti3C2QDs/BiOBr-OVs composite photocatalyst demonstrates significant potential for environmental applications.