This work reported a novel ternary heterogeneous photocatalyst NaYF4:Yb,Er,Tm@Bi@BiOI (NBEG-6h). NBEG-6h exhibits broad-spectrum absorption from ultraviolet to near-infrared. The elimination efficiency of BPA by NBEG-6h under simulated sunlight and near-infrared light irradiation was 88% (24 min) and 93.9% (160 min), respectively. It also has the universality of degrading various pollutants, good reusability and stability. The exceptional photocatalytic activity can be attributed to the absorption of near-infrared light by NaYF4:Yb,Er,Tm, which improves the total efficiency of sunlight utilization. The localized surface plasmon resonance effect of Bi nanoparticles enhances the light absorption performance of the heterostructure. Furthermore, combining Bi and BiOI accelerates carrier migration and improves the separation efficiency of photogenerated electron-hole pairs. h+, ·O2− and 1O2 play the pivotal roles during the photocatalytic process. This research offers new insights into the design, development, and mechanism understanding of full-spectrum-driven heterostructure photocatalysts. It provides an environmentally sustainable approach to the treatment of harmful organic pollutants.