Due to the wide usability of thermoelectric generators (TEG) in the industry and research fields, it is plausible that mismatching conditions are present on the thermal surfaces of a TEG device, which induces negative-performance effects due to uneven surface temperature distributions. For this reason, the objective of this study is to characterize numerically the open-circuit electric output voltage of a TEG device when a mismatching condition is applied to both the cold and hot sides of the selected N and P-type semiconductor material Bi0.4Sb1.6Te3. A validated numerical simulation paired with a parametric study is conducted using the Thermal-Electric module of ANSYS 2020 R1, for which different thermal boundary and mismatching conditions are applied while considering the temperature-dependent thermoelectrical properties of the N and P-type material. The results show an inverse relationship between the open-circuit voltage and the mismatching temperature difference. When a mismatching condition is applied on the hot side of the TEG device, the temperature-dependent electrical resistance has lower values, deriving in higher voltage results (linear tendency) compared to a mismatching condition applied to the cold side (non-linear tendency).