This study investigates the deposition of Cu2ZnSnS4 (CZTS) thin films on fluorine-doped tin oxide (FTO) and soda-lime glass (SLG) substrates using radio frequency (RF) sputtering at varying temperatures. A comprehensive characterization employing multiple analytical techniques was conducted. X-ray diffraction (XRD) analyses confirmed the amorphous nature of CZTS films being deposited up to 200 °C, while higher temperatures promoted increased crystallinity, with the presence of (112) and (220) planes observed at 300 °C and 400 °C. Rietveld refinement using Profex software revealed an increase in crystallite size with deposition temperature for films grown at 300 °C and 400 °C. Optical characterization through UV–vis spectroscopy unveiled a decrease in band gap energy with increasing deposition temperature, while the Urbach energy, associated with defects and imperfections, exhibited an inverse relationship with band gap and temperature. Experimental current–voltage (I-V) measurements using a Keithley source meter showed variations in the ideality factor with deposition temperature. SCAPS-1D simulations were performed to model the FTO/CZTS interface, incorporating experimental parameters. The simulated I-V behavior demonstrated a transition from recombination to diffusion-dominated current above 1.3 V forward bias. Simulations yielded higher ideality factors due to increased contributions from recombination and diffusion currents. Overall, this study provides insights into the growth, structural, optical, and electrical properties of CZTS thin films deposited by RF sputtering, enabling a comprehensive understanding of the FTO/CZTS heterojunction characteristics and their dependence on deposition temperature.