Mesoporous NH2-MIL-125(Ti)@Bi2MoO6 core-shell heterojunctions with surface defects were fabricated through a facile solvothermal method. The mesoporous core-shell structure with a large relative surface area of 87.7 m2 g−1 and narrow pore size of 8.2 nm extends the photoresponse to the range of visible light due to the narrow band gap of ∼1.89 eV. The visible-light-driven photocatalytic degradation efficiency of highly toxic dichlorophen and trichlorophenol were 93.28 and 92.19%, respectively, and the corresponding rate constants were approximately 8 and 17 times higher than the rates achieved by pristine NH2-MIL-125(Ti). The photocatalytic oxygen production rate was increased to 171.3 µmol g−1. Recycling for several cycles indicates high stability, which is favorable for practical applications. The excellent photocatalytic performance can be ascribed to the formation of the core-shell heterojunctions and to the surface defects that favor charge separation and visible light absorption; the mesoporous structure offers an adequate number of surface active sites and mass transfer. This novel mesoporous core-shell photocatalyst will have potential applications in the environment, and this strategy offers a new insight into fabrication of other high-performance core-shell structure photocatalysts.