Fullerene (C₆₀) loaded in macroporous carbon (C₆₀/MPC) composite by π–π stacking was prepared and attached on a glassy carbon electrode. A novel partially reduced C₆₀-grafted MPC (K₃C₆₀/MPC) composite was fabricated when the modified electrode was subjected to cyclic voltammetric scans in KOH solution. The formation of these composite materials was verified by detailed characterization (e.g., Fourier transform infrared, X-ray photoelectron spectroscopy, energy dispersive X-ray) analyses. TEM revealed that the aggregates of C₆₀ with diameters of about 9.4 nm and partially reduced C₆₀ moieties aggregates of ∼1.8 nm in diameter were finely dispersed on the MPC surface. The resultant K₃C₆₀/MPC was used as a conductive film to significantly improve the transport of electrons and exhibited favorable electrochemical activity in terms of good stability and excellent electro-catalytic capability. More importantly, the electrochemical behavior of the as-prepared composite towards nitroaromatic compounds was assessed and a novel electrode system using linear sweep voltammetry for the preparation of an electrochemical sensor platform is proposed.