The capacitance–voltage (C–V) method is frequently used to evaluate the net doping of thin-film solar cells, an important parameter for the function of solar cells. However, complex materials such as kesterites are challenging to characterize. To minimize ambiguity when determining the apparent doping concentration (${{N_{A}}}$) of Cu2 ZnSnS4 (CZTS), we fabricated and investigated different structures: CZTS/ZnS metal–insulator–semiconductor (MIS) device, stand-alone CZTS and ZnS metal-sandwich structures, and CZTS solar cells. Characterization was carried out by means of admittance spectroscopy (AS) and C– V measurements. ZnS exhibits excellent intrinsic properties, and with the high-quality MIS sample we managed to successfully isolate the capacitive response of the CZTS itself. ${N_{A}}$, as extracted from the MIS structure, is found to be more reliable and four times higher compared with the solar cell, impacting any estimated collection efficiency substantially. Data herein presented also show that CZTS has a substantial low-frequency dispersive capacitance and the extraction of ${N_{A}}$ depends on the chosen measurement frequency, symptoms of presence of deep defects. Furthermore, the CZTS/ZnS MIS structure is strongly resilient to leakage currents at both forward and reverse voltage bias where contribution from deep defects is minimized and maximized, respectively.