A novel family of bioinspired manganese(II) complexes bearing chiral aminopyridine ligands that possessed additional aromatic groups and strong donating dimethylamino groups were synthesized and characterized. These manganese complexes exhibited efficient and improved activities in the asymmetric epoxidation of various olefins, such as styrene derivatives (up to 93% ee) with H₂O₂ as the oxidant, even with a catalytic amount of carboxylic acid as the additive.