We have investigated characteristics of ZnSe epilayer grown by molecular beam epitaxy(MBE) on semi-insulating(SI) GaAs by using surface photovoltage(SPV). The measurements of SPV were performed with illumination intensity and modulation frequency. The bandgap energy of ZnSe epilayer was determined from derivative surface photovoltage (DSPV). The five states were observed at room temperature(RT), and those states relate to the impurity and defect formed hetero-interface of ZnSe and GaAs during the sample growth. The observed states represented as a tendency of typical extrinsic transition on the increasing illumination intensity. The 1s and 2s signals related to the excitonic absorption were not observed at RT, but those were presented with the splitted of two peaks in the SPV at 80 K. From the modulation frequency dependence, we obtained the junction conductance and capacitance of the sample.