alpha-Aziridinyl carbenium ion as an intermediate was observed for the first time from the reaction of aziridin-2-yl arylmethanol with Lewis acid BF3 center dot OEt2. This intermediate was further reacted with various nucleophiles including electron-rich arenes to afford the adducts in highly stereoselective manner as singly isomers. alpha-Aziridinyl carbenium ion intermediate was observed spectroscopically as a crucial intermediate, and density functional theory (DFT) calculations show the origin of stereoselectivity based on thermodynamic preference for the reaction.