The existence of intermolecular or intramolecular N center dot center dot center dot H-O or N-H center dot center dot center dot O hydrogen bonding in three series (series 1, substituted 1-aminoalkyl-2-naphthols: R = H, Me, Et, Pr, i-Pr; series 2, Substituted 1-alpha-aminobenzyl-2-naphthols: H, p-OMe, p-F, p-Cl, p-Br, p-NO2, p-Me; series 3, substituted 2-alpha-aminobenzyl-1-naphthols: R = H, p-Me, p-F, p-Br, p-OMe, m-NO2, m-Br) are Studied by NMR spectroscopy and computed at the DFT level of theory [B3LYP/6-311+G(d,p)]. The correct nature of the H-bond was assigned unequivocally both experimentally and computationally by potential energy scans rotating the involved dihedral angles. We investigated the effects Of substituents on the strength of the H-bond by evaluating the corresponding hypercon ugative stabilization energy n(lonepair) -> sigma*X-H and Hammett substituent constant plots. By this means, steric and electronic substituent effects could be easily quantified and separated.