Graphitic carbon nitride (CN)-based materials were synthesized using melamine, urea, guanidine carbonate, and thiourea as precursors via pyrolysis. The synthesized materials underwent comprehensive characterization employing techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption test. These materials were evaluated for their performance as cathodes with platinum sheet electrodes as anodes in the selective electrocatalytic reduction of Sn(Ⅳ) in an acid solution. During the reduction of Sn(Ⅳ) to Sn(Ⅱ), Sn(Ⅱ) can also be reduced to Sn due to the similar reduction potentials of Sn(Ⅱ) and Sn(Ⅳ). The deposition of Sn on the cathode diminishes the electrode conductivity efficiency. Therefore, the electrode material must fulfill the dual requirements of reducing Sn(Ⅳ) to Sn(Ⅱ) while preventing the reduction of Sn(Ⅱ) to Sn. In comparison to conventional cathode materials such as copper plates, graphite plates, ruthenium iridium titanium plates, and platinum plates, the CN demonstrated superior performance in the selective electrocatalytic reduction of Sn(Ⅳ) in an acidic solution. In addition, CN exhibited a lower potential in a dual-electrode electrolytic cell and maintained stability under acidic conditions, enabling the selective reduction of Sn(Ⅳ) to Sn(Ⅱ).