A graphene-Nafion composite film was fabricated on the glassy carbon electrode (GR-NF/GCE), and used for simultaneous determination of paracetamol (PAR), aspirin (ASA) and caffeine (CAF). The electrochemical behaviors of PAR, ASA and CAF were investigated by cyclic voltammetry and square-wave adsorptive anodic stripping voltammetry. By using stripping one for simultaneous determination of PAR, ASA and CAF, their electrochemical oxidation peaks appeared at +0.64, 1.04 and 1.44 V, and good linear current responses were obtained with the detection limits of 18 ng mL⁻¹ (1.2×10⁻⁹ M), 11.7 ng mL⁻¹ (6.5×10⁻⁸ M) and 7.3 ng mL⁻¹ (3.8×10⁻⁸ M), respectively. Finally, the proposed electrochemical sensor was successfully applied for quantifying PAR, ASA and CAF in commercial tablet formulations.