Cu2ZnSnSe4 (CZTSe) thin film has been synthesized onto silicon substrates by liquid phase epitaxial growth for the first time in which Au/CZTSe/n-Si/Al heterojunction was successfully fabricated by this technique. The crystal structure and morphology of the CZTSe film were characterized by field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The I-V characteristics of the CZTSe/n-Si heterojunction in the dark have been studied at different temperatures ranged from 298 to 398 K to determine the diode parameters such as the rectification ratio, series and shunt resistances (RR, Rs and Rsh resp.), the effective barrier height (ϕb) and the diode ideality factor (n). The CZTSe/n-Si heterojunction shows an excellent rectification behavior. The ideality factor n, series resistance RS, and shunt resistance RSh, were decreased with increasing the temperature. The photovoltaic constants such as VOC, JSC, fill factor and the efficiency of CZTSe/n-Si heterojunction have been calculated from the I-V characteristics under illumination. The CZTSe/n-Si heterojunction exhibits efficiency about 3.42% at room temperature. The dielectric measurements proved that the CZTSe/n-Si heterojunction device shows the behavior of two forward biased Schottky diodes.