The electrocatalytic oxidation behaviors and electrochemical determination of glutathione（GSH） were investigated at nano-TiO2-caffeic acid modified carbon paste electrode（nano-TiO2-CFA/CPE）.The experimental results indicated that GSH showed a very poor electrochemical response at CPE and nano-TiO2/CPE,but GSH at nano-TiO2-CFA/CPE exhibited a better electrocatalytic activity than that at CFA/CPE.The kinetic properties of GSH were discussed at nano-TiO2-CFA/CPE by cyclic voltammetr（CV）and chronoamperometry（CA）.The catalytic oxidation peak current of GSH versus its concentration had a good linear relationship in the concentration range of 9.0×10-6 -1.0×10-3 mol·L-1 with a correlation coefficient of 0.997 5,and a detection limit of 8.85×10-7 mol·L-1 by linear sweep voltammetry（LSV）.The method was applied in the determination of GSH contents in real samples with satisfactory results.