New chiral Mn(III)–salen complexes 1a–e and 2a–e were synthesized from the reaction of C₂-symmetric chiral salen ligands and Mn(CH₃COO)₂·4H₂O under an inert atmosphere followed by aerobic oxidation. These complexes were obtained in 91–96% yields and characterized by HRMS, FT-IR, UV-visible spectroscopy, TGA, and elemental analysis. The chiral Mn(III)–salen complexes 1a–e and 2a–e were evaluated in the asymmetric epoxidation of styrene using NaOCl as an oxidant in ethyl acetate as a green solvent. The chiral Mn(III)–salen complexes 1b and 2b (2 mol%) catalyzed the asymmetric epoxidation of substituted styrenes and chromenes to afford the corresponding epoxides in 95–98% yields with 29–88% ee's. The catalysts 1b and 2b were recovered and reused for up to 2 and 3 runs, respectively, in the asymmetric epoxidation of styrene, and the yield of styrene oxide gradually decreased but the ee was consistent.