Here we demonstrate the synthesis of a novel chiral Co(III)–salen complex supported functionalized 2D-hexagonal mesoporous silica material Co(III)@AFS-1. This material has shown excellent catalytic activity for the regio- and enantioselective asymmetric ring opening (ARO) of terminal and meso epoxides using various aromatic as well as cyclic amines to produce chiral β-amino alcohols having very good enantioselectivities (ee > 99%) at ambient temperature under solvent-free neat conditions.