In this paper, we present results of the electrical characterization of n-Si/p-Cu-Zn-Se hetero-structure. Sputtered film was found in Se-rich behavior with tetragonal polycrystalline nature along with (112) preferred orientation. The band gap energy for direct optical transitions was obtained as 2.65 eV. The results of the conductivity measurements indicated p-type behavior and carrier transport mechanism was modelled according to thermionic emission theory. Detailed electrical characterization of this structure was carried out with the help of temperature-dependent current-voltage measurements in the temperature range of 220-360 K, room temperature, and frequency-dependent capacitance-voltage and conductance-voltage measurements. The anomaly in current-voltage characteristics was related to barrier height inhomogeneity at the interface and modified by the assumption of Gaussian distribution of barrier height, in which mean barrier height and standard deviation at zero bias were found as 2.11 and 0.24 eV, respectively. Moreover, Richardson constant value was determined as 141.95 Acm(-2)K(-2) by means of modified Richardson plot.