Using meso-terakis(4-methoxyl-3-sulfonatophenyl) porphyrin(T(4-Mop)PS4) as an electrochemical probe,a new electroanalytical method for the determination of bovine serum albumin (BSA) was established based on the interaction of BSA with T(4-Mop)PS4.A good linear relationship was obtained between the variation of peak current and concentration of BSA in the range of 2.0×10-6-1.0×10-5 mol?L-1.The limit of detection(LOD) was 1.2×10-6 mol?L-1 and the relative standard deviation(RSD,n=8) for 50×10-6 mol?L-1 BSA was 20%.The supramolecular complex of T(4-Mop)PS4 with BSA was studied by three different methods,including spectrophotometry,fluorometry and linear sweep voltammetric(LSV) methods.The binding ratio and binding constant of T(4-Mop)PS4 with BSA were obtained.The experimental data demonstrated that T(4-Mop)PS4 could form a 1∶1 stable supramolecular complex with BSA,and hydrophobic interaction is the main reaction between them.