Polycrystalline thin film CdS/CdTe heterojunction solar cells are important candidates for large scale photovoltaic applications. In this work we use a C-V (capacitance vs. voltage) theoretical method for the determination of the interface charge density sigma and band discontinuity Delta Ev of the CdS/CdTe heterojunction. The methodology is based on three cardinal equations: i) line up of the bands relative to the common Fermi level (at equilibrium) or the quasi-Fermi level (when voltage is applied), ii) charge neutrality and iii) the total capacitance of the heterostructure. We used CdS/CdTe solar cells, grown in our laboratory by the chemical bath deposition (for CdS film) and the close space vapor transport (for CdTe film) techniques. The interface parameters sigma, and Delta Ev are determined from C-V fitting between the calculated and the measured curve. The methodology presented in this study is general and can be applied to semiconductorsemiconductor and semimetal-semiconductor heterojunctions. (C) 2009 Elsevier B.V. All rights reserved.