Designing a material with the advantage of adsorption-enrichment and photocatalysis degradation has great practical significance in water treatment. BiPO4, as a promising photocatalyst for environmental purification, still suffers from small specific surface area and relative low photocatalytic activity. Herein, BiPO4-SiO2 hybrid hydrogels were successfully fabricated by facile two-step methods. BiPO4 nanorods are uniformly compounded with SiO2 spheres, and the specific surface area of BiPO4 is enhanced by 2.3 times after forming a network structure. 90% BiPO4-SiO2 hybrid hydrogel presents the highest photocatalytic degradation activities, which is 3.4 times that of pure BiPO4. The total organic carbon removal ability of BiPO4 is also enhanced by 1.1 times after constructing a hybrid hydrogel. The pollutant removal enhancement of BiPO4-SiO2 hybrid hydrogel can be attributed to the synergistic effect of adsorption-enrichment and photocatalytic degradation. Our results may provide a promising way to greatly enhance the pollutant removal performance of BiPO4, which may promote the industrial application of BiPO4.