This research focuses on improving the photoelectrochemical performance of binary heterostructure Ag2S/ZnO NRs/ITO by manipulating synthesis conditions, particularly the concentrations of sliver nitrate AgNO3 and thiourea CS(NH2)2. The photoelectrochemical performance of Ag2S/ZnO nanorods on indium tin oxide (ITO) nanocomposite was compared to pristine ZnO NRs/ITO photoanode. The hydrothermal technique, an eco-friendly, low-cost method, was used to successfully produce Ag2S/ZnO NRs at different concentrations of AgNO3 and CS(NH2)2. The obtained thin films were characterized using field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-vis), and photoelectrochemical studies (PECs). We observed that there was an enhancement in absorbance in the visible region and effective photoelectron transfer between the Ag2S/ZnO NRs/ITO photoelectrode and the electrolyte Red-Ox when illuminated with 100 mW cm−2. Increasing the concentration of AgNO3 caused a remarkable decrease in the optical bandgap energy (Eg) values. However, we noticed that there was an unstable trend in Eg when the concentration of CS(NH2)2 was adjusted. The photoelectrochemical studies revealed that at a bias of 1.0 V, and 0.005 M of AgNO3 and 0.03 M of CS(NH2)2, the maximum photocurrent of the Ag2S/ZnO NRs/ITO photoanode was 3.97 mA/cm2, which is almost 11 times that of plain ZnO nanorods. Based on the outcomes of this investigating, the Ag2S/ZnO NRs/ITO photoanode is proposed as a viable alternative photoanode in photoelectrochemical applications.