Herein, NaGdF4:Yb,Er nanoparticles were anchored on a Material of Institute Lavoisier (MIL-101). In the well-defined heterostructure, MIL-101/NaGdF4:Yb,Er, the absorption and fluorescence could be tuned, and the composite facilitated the separation of photogenerated electron-hole pairs. Moreover, the heterostructure displayed a higher photocurrent and better degradation ability for Rhodamine B that its individual components owing to its synergistic effect.