A green, and highly regioselective approach for the synthesis of β–amino alcohols (15–98%) via aminolysis of epoxides by varied amines using LiBr under aqueous mortar–pestle grinding conditions has been described. Use of a mild catalyst, ordinary grinding, time economy, cost effectiveness, complete regioselectivity, and a very good to excellent yield of desired products makes this process an attractive route for the synthesis of biologically significant pharmacophores. Further, the developed protocol has been successfully extended for the synthesis of novel series of β–amino alcohols (3r–3ad) bearing benzofused 1,2,3–triazole heterocycle with complete regioselectivity. The structure of the synthesized molecules has been characterized by spectroscopic techniques such as 1H nuclear magnetic resonance (NMR), 13C NMR, and mass spectroscopy.