A novel visible-light driven 3D porous network structure rGO-Ag@Ag3PO4 (RAA) hydrogel composite photocatalyst with a synergistic effect of adsorption enrichment and photocatalysis degradation has been synthesized by a facile method and characterized by XRD, SEM, TEM, EDS, FTIR, DRS, UV-vis, TG, Raman, and XPS. RAA hydrogel photocatalyst with 3D porous network structure is not only favorable to increasing the absorption property for organic pollutants owing to a larger surface area and pi-pi conjunction property, but also promotes the separation and transformation of electron-hole pairs due to the good conductivity performance. The RAA hydrogel composite photocatalyst has exhibited the excellent removal capacity of organic pollutants which were about 1.94 and 1.10 times higher than those of bare Ag3PO4 for the removal of MB and 2, 4-CDP in the dynamic system, respectively. The enhancement of removal efficiency was due to a synergistic effect of adsorption enrichment and photocatalysis degradation. The removal rate of RAA hydrogel composite photocatalyst has only a little decrease from 76.04% to 68.51% for 60 h of the photoreaction, showing the relatively good stability. The trapping experiment and ESR showed the main active species were holes.