Three-dimensional PANI/CdSNRs-SiO2 hydrogel (CdS NRs-PANI-SiO2) was synthesized by loading polyaniline (PANI) onto the semiconductor CdS nanorods (NRs) surface and loading the binary complex on SiO2 gel. The structure, optical properties, and electrochemical properties of the composite were studied in detail. The hydrogen production amount of CdS NRs-PANI (3%)-SiO2 (20%) increased in comparison with CdS NRs and reached 43.25 mmol/g in 3 h under visible light. The three-dimensional structure of SiO2 hydrogel increased the specific surface area of the catalyst, which was conducive to exposing more active sites of the catalyst. In addition, the conductive polymer PANI coated on CdS NRs played the role of conductive charge and effectively inhibited the photo-corrosion of CdS NRs. In addition, the recovery experiment showed that the recovery rate of the composite catalyst reached 90% and hydrogen production efficiency remained unchanged after five cycles, indicating that the composite catalyst had excellent stability.