Abstract: The axial coordination between Tris(pentafluorophenyl)corrole (TPFC)Mn(Ⅲ) and DNA bases was studied with the DFT/B3LYP method. The results showed that different coordination atoms of the same base led to different degrees of coordination binding with (TPFC)Mn(Ⅲ). The O atoms exhibited stronger coordination binding ability than the N atoms. The interaction between (TPFC)Mn(Ⅲ) and A = T or C≡G base pairs of DNA occurred mainly through intercalation mode. Whether intercalation or external binding, the coordination ability of adenine (A) or guanine (G) was stronger than that of thymine (T) or cytosine (C) for A≡T or C≡G base pair.