Four new-type N,N′,O,O′-Salen ligands were synthesized by the condensation of o-aminophenol with dialdehyde or diketone, and new-type Salen-Mn catalysts (C1, C2, C3, C4) were synthesized by ligand coordination reaction with Mn(Ac)2·2H2O. The catalysts were characterized by FT-IR, UV-Vis and coordination titration and the structure of the ligands was optimized by using Hartree-Fork/3-21G. The catalytic performance of the catalysts was investigated by epoxidation. The results indicated that the catalytic activity of the new-type Salen-Mn catalysts is related to the structure, the new-type catalyst C1 and the traditional catalyst C5 have considerable catalytic activity in the epoxidation reactions due to their similar structure, but the catalytic activity of the new-type catalysts C2, C3, C4 is weaker than that of C1 because of the different structure with C1 and C5.