Nanocomposites of the binary transition metal sulfide Zn-Co-S/graphene (Zn-Co-S@G) were synthesized through a one-step hydrothermal method. They may be useful in the construction of an electrochemical immunosensor for carbohydrate antigen 19-9 (CA19-9) detection. Zn-Co-S dot-like nanoparticles uniformly covered the surface of graphene to form an interconnected conductive network, ensuring strong interaction between transition metal sulfide and graphene, which can expose numerous electroactive sites leading to the improvement of the amplified electrochemical signal toward a direct reduction of H₂O₂. Thus, the construction of an electrochemical immunosensor using Zn-Co-S@G nanocomposites showed outstanding sensing properties for detecting CA19-9. The constructed electrochemical immunosensor exhibited a good linear relationship in the range of 6.3 U·mL⁻¹–300 U·mL⁻¹, with the limit of detection at 0.82 U·mL⁻¹, which makes it a promising candidate for an electrochemical immunosensor.