In order to improve the photocatalytic performance of TiO2 and expand its absorption range in the visible light region, depositing noble metals, constructing the p-n heterojunction and controlling the morphology were used to modify TiO2. First, the TiO2 photocatalyst with a three-dimensional ordered macroporous structure was prepared by vacuum impregnation combined with calcination, and then the 3DOM Ag/BiOI/TiO2 composites were successfully prepared by the in-situ deposition and photoreduction. The characterization results show that the composites present a large number of open and transparent pore structures. The pore wall is formed by stacking TiO2 nanoparticles, with BiOI and Ag nanoparticles evenly distributed on the surface of the pore wall and in the macroporous framework, which expands the specific surface area of 3DOM TiO2 and provides more active sites for the reaction. The introduction of BiOI and Ag expands the visible light response range and improves the light utilization efficiency. Furthermore, the formation of the Schottky barrier and the internal electric field formed by the p–n heterojunction effectively promotes the interfacial electron transfer and suppress the electron–hole recombination, thereby generating more active species during the photocatalytic process. The experimental results of multi-mode photocatalytic degradation of methyl orange (MO) also show that 3DOM Ag/BiOI/TiO2 photocatalyst has the best photocatalytic degradation activity. In addition, different samples were tested for hydrogen production by photolysis of water under simulated sunlight conditions, and the results show that 3DOM Ag/BiOI/TiO2 has the best hydrogen production ability of photolysis of water. The excellent performance of multi-modal photocatalytic degradation of organic pollution and high photohydrogen production activity in 3DOM Ag/BiOI/TiO2 composites is attributed to the synergistic effect between the introduction of metallic Ag, the unique 3DOM structure, and the p–n heterojunction.