Ternary metal sulfides with suitable band gaps, high physicochemical stability, and unique two-dimensional (2D) nanostructures are expected to be the next-generation high-performance gas sensors following the MOS type. Doping engineering is utilized as an effective strategy to improve the semiconductor surface activity and enhance its gas-sensitive properties. In this paper, the energy band structure and surface chemical oxygen of ZnIn2S4 (ZIS) materials was tuned by selectively introducing substitutional Cd to replace the Zn sites in ZIS crystals. Meanwhile, the introduction of Cd-ions brings more abundant S vacancy defects, enhances the acid-base interactions at the interface, and pushes the extent of surface redox reactions. In addition, by combining the strong adsorption of ZIS to triethylamine, the CdxZn1-xIn2S4 nanosheets achieved highly improved sensing properties, including better response (63.38–100 ppm), enhanced selectivity (STEA/sother = 12.9), and accelerated response/recovery (4 s/32 s). The results confirm the feasibility of developing low-cost, high-performance 2D metal sulfide gas sensing materials through rational structural design and optimization.