The preferential Li + solvation in aqueous ammonia has been revisited by performing an extended ab initio QM/MM MD simulation, in which the QM region’s size was enlarged to 4.2Å radius. The use of larger QM region leads to a clear water preference with an arrangement of Li + [(H 2 O) 4 ][(H 2 O) 4 ] type, compared to the preferred Li + [(H 2 O) 3 NH 3 ][(H 2 O) 4 (NH 3 ) 2 ] structure obtained by a previous QM/MM simulation using a small QM region not comprising the second solvation shell. The observed discrepancies clearly demonstrate the importance of quantum chemical treatment of the second shell in order to obtain a reliable and accurate description of this solvated ion.