The Co(salen) ([LCo(II)]) mediated hydrofunctionalization of alkenes is a highly significant method for forming enantioselective products. In this work, we conducted comprehensive computational investigations to gain insights of the reaction mechanism. The orbital analysis and intrinsic bond orbital analysis (IBO) were utilized to unravel the flow of electrons during the progress of the reaction. We explored various spin state surfaces to understand the possible pathways for the reaction. Initially, [LCo(II)] reacts with an oxidant tertbutyl peroxybenzoate, yielding [LCo(III)OC(O)Ph] and [LCo(III)O