Electrical properties of solution processed Cu2ZnSnS4 (CZTS) compound semiconductor thin film structures on molybdenum (Mo) coated glass substrates are investigated using Mott-Schottky and Impedance spectroscopy measurements at room temperature. These measurements are carried out in sodium sulfate (Na2SO4) electrolytic medium at pH ~ 9.5. The inversion/depletion/accumulation regions are clearly observed in CZTS semiconductor-Na2SO4 electrolyte interface and measured flat band potential is ~-0.27?V for CZTS thin film electrode. The positive slope of the depletion region confirms the intrinsic p-Type characteristics of CZTS thinfilms with ~ 2.5× 1019 holes/m3. The high frequency impedance measurements showed ~ 30 Ohm electrolyte resistance for the investigated configuration. © 2016 Author(s).