A series of Mn-complexes with tetradentate N-4 ligands, introducing aromatic groups into 2-pyridylmethyl positions of N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine (mep), N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)cyclohexane-trans-diamine (mcp), have been synthesized and applied for epoxidation of olefins using H2O2 as the oxidant. The Mn-complexes still possessed an octahedral mononuclear structure in a cis-alpha topology. These complexes showed good regioselectivity, high yields and turnover frequency (even up to 228,000 h(-1)) with low catalyst loading (0.1-0.01 mol%) for epoxidation of a family of olefins (including internal aromatic olefins, internal and terminal aliphatic olefins and diolefins). (C) 2011 Elsevier B.V. All rights reserved.