The potential of photocatalytic CO2 conversion is significant for the production of fuels and chemicals, while simultaneously mitigating CO2 emissions and addressing environmental concerns. Despite the current drawbacks of single metal-based photocatalysts, such as lower performance, uncontrollable selectivity, and instability, this study focuses on the synthesis of Ag3VO4 nanorods using the sol–gel method. The goal is to create a highly effective catalyst for visible light-responsive CO2 conversion. The successful synthesis of Ag3VO4 nanorods with a nanorod structure, functional under visible light, resulted in the highest yields of CH4 and dimethyl ether (DME) at 271 and 69 µmole/g-cat, respectively. The optimized Ag3VO4 nanorods demonstrated performance improvements, with CH4 and DME production 6.4 times and 4.5 times higher than when using V2O5 samples. This suggests that Ag3VO4 nanorods facilitate electron transfer to CO2, offer short pathways for electron transfer, and create empty spaces within the nanorods as electron reservoirs, enhancing the photoactivity. The prolonged stability of Ag3VO4 in the CO2 conversion system confirms that the nanorod structure provides controllable selectivity and stability. Therefore, the fabrication of nanorod structures holds promise in advancing high-performance photocatalysts in the field of photocatalytic CO2 conversion to solar fuels.