We determined antioxidant activity of alkaloids in Caulis Mahoniae by DPPH. We isolated berberine, jatrorrhizine, palmatine, columbamine and stepharanine with pHzonerefining CCC. We also evaluated external antioxidant capability of dominant alkaloids in Caulis Mahoniae through DPPH free radical scavenging rate determination of total alkaloids and monomeric alkaloids. Results show that linear positive correlation exists for the concentration and absorbance of DPPH solution from 0 to 25 μg/mL. IC50 of total alkaloids, berberine, jatrorrhizine, palmatine, columbamine and stepharanine are respectively 0.07, 0.32, 0.24, 0.20, 0.18, and 0.59 mg/mL, so alkaloids of Caulis Mahoniae has certain antioxidant capability. It will be enhanced with the increase of alkaloids concentration. Moreover, antioxidant ability of total alkaloids is higher than that of monomeric compounds. Antioxidant activity of Caulis Mahoniae alkaloids may be synergistic effect.