Herein, graphite/Ag/AgCl nanocomposite is introduced as a new electrocatalyst material for the electrocatalytic oxidation of oxalic acid. Graphite/Ag/AgCl was synthesized by electroless deposition of nano-sized metallic silver and then silver chloride on graphite powder. The material obtained was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Energy-dispersive X-ray spectroscopy. The nanocomposite was mixed with n-eicosane as binder and used as carbon paste electrode for electrocatalytic oxidation of oxalic acid (OA). The graphite/Ag/AgCl nanocomposite electrode showed good catalytic activity for the electroxidation of oxalic acid in H3PO4 solution (0.05 mol L−1), leading to a distinct decrease in anodic overpotential (100 mV) and a substantial increase in anodic peak current (about 10 times), in comparison with the unmodified carbon paste electrode. Using the developed nanocomposite electrode and differential pulse voltammetry method, it became possible to determine oxalic acid in the concentration range of 0.01–0.75 mmol L−1 with detection limit of 3.7 × 10−6 mol L−1. The electrode showed very high sensitivity of 1341.3 μA mM−1 cm−2 which is remarkably better than the previously reported oxalic acid sensors. Thanks to high sensitivity and good selectivity of the electrode, the proposed method was successfully applied for the determination of OA in human urine and spinach samples. The satisfactory results obtained, confirmed the applicability of this sensor in the practical analysis.