Photoelectrochemical cell technology is one of the simplest technologies, which converts light energy directly into electricity. The synthesis of cadmium sulfide (CdS) nanocrystals (NCs) was performed by the facile hot injection method. The NCs were characterized by different techniques such as XRD, Raman, UV-Vis, FESEM, and XPS. The XRD pattern confirms the phase pure hexagonal CdS NCs. The band gap of NCs calculated from the UV-Visible spectrum is at 2.40 eV, indicating good absorption in the visible spectrum. XPS analysis confirmed the presence of individual elements in CdS NCs. The CdS thin-films having different thicknesses were prepared on FTO substrates using the spin coating technique. Photoelectrochemical (PEC) investigation of CdS NCs thin-films photoelectrodes was performed by varying its thickness. The increase in the thickness of thin-films increased photocurrent density.