By substituting Zn1‐xMgxO (ZMO) for the conventional CdS buffer layer, the CZTSSe solar cells with the efficiency of 11.2% was obtained in the work, which could be attributed to the conduction band regulation in the heterojunction. An appropriate conduction band offset (CBO) value can effectively reduce non‐radiative recombination loss of charge carriers at the interface, thereby improving the open‐circuit voltage (Voc). In this study, ZMO buffer layer with the optical bandgap (Eg) ranging from 3.34 eV to 3.90 eV was applied to enhance the CBO in the heterojunction from 0.14 eV to 0.72 eV. The ZMO‐buffered solar cells exhibit higher Voc and short current density (Jsc) compared to CdS‐buffered cells. The optimal efficiency of 11.2% was obtained in CZTSSe solar cell with the CBO of 0.27eV, Jsc of 39.0 mA/cm², fill factor (FF) of 69.6%, and Voc of 412 mV.This article is protected by copyright. All rights reserved.