The interaction of glucose oxidase (GOD) and four photosensitizers, ZnPcS4, ZnPc(NHCH2COOH)(4), ClAlPcS, and porphyrine-like, were monitored by capillary electrophoresis. GOD, its degenerated products and photosensitizers were simultaneously separated in a buffer of 300 mmol/L berate at pH 8.5 on a commercial CE instrument. By comparison of the electropherograms of GOD as well as the mixture of GOD and photosensitizers without/with irradiation of different time, it was found that photosensitized oxidations between GOD and different photosensitizers have different reaction mechanisms and kinetics.