In this study, porphyrin-based zirconium MOF (MOF-525)/macroporous carbon (MPC) composites were successfully prepared by conventional solvothermal reaction for the first time. Structural characteristics and experimental studies show that MOF-525/MPC composites combine the advantages of MOF-525 and MPC, which possess high BET surface area, large pore size, excellent conductivity and high catalytic activity of porphyrin. A novel electrochemical sensor based on MOF-525/MPC was fabricated, which presents superior electrocatalytic activity to the oxidation of luteolin. Meanwhile, the reaction mechanism of luteolin on MOF-525/MPC modified glassy carbon electrode (GCE) was researched. Electrochemical detection indicates that the luteolin sensor displays two linear responses in the ranges of 5 nM-0.1 mu M and 0.1-5 mu M, with a low detection limit of 0.35 nM. The proposed sensor was also used for the determination of luteolin in actual samples, and the results are satisfactory, revealing great potential of the sensor in practical applications.