Industrial dyes contained a wide range of organic compounds that could affect the environment and high dimensional challenges to humans. In recent years, the environmentally safe and inexpensive quaternary copper-based chalcogenide Cu2ZnSnS4 (CZTS) has emerged as a material for photovoltaics and photocatalysis. CZTS nanoparticles were prepared in this investigation using the hydrothermal route at 210 °C for 24 h without the addition of a surfactant or capping agents. Rhodamine B (RhB), a carcinogenic dye, was degraded using the synthesized material through a photocatalytic process. The structural, morphological, optical, and photocatalytic characteristics of CZTS nanoparticles were examined using X-ray diffraction (XRD), Raman spectroscopy, Field emission scanning electron microscopy (FE-SEM), and UV-vis spectroscopy. The average particle size of CZTS is found to be 31 nm with crystalline nature have been characterized by XRD. The results demonstrate that the synthesized sample has mixed morphological structures such as clew-like and flower-like structures and a bandgap of 1.50 eV. CZTS nanoparticles were used as photocatalysts under direct sunlight for Rhodamine B degradation, with the fastest degradation efficiency of 72% at 50 minutes. The results show that surfactant-free hydrothermally synthesized CZTS nanoparticles are a very promising material for the degradation of RhB dye due to the rapid degradation rate and high degradation efficiency.