The stability of two stable cis-enol forms in two categories of β-diketones, including para-substituted of trifluorobenzoylacetone (X-TFBA) and 1-aryl-1,3-diketone malonates (X-ADM, X: H, NO2, OCH3, CH3, OH, CF3, F, Cl, and NH2) has been obtained by different theoretical methods. According to our results, the energy difference between the mentioned stable chelated enol forms for the titled compounds is negligible. The theoretical equilibrium constants between the two stable cis-enol of the mentioned molecules are in excellent agreement with the reported experimental equilibrium constant. In addition, the effect of different substitutions on the intramolecular hydrogen bond strength has been evaluated. The correlation between Hammett para-substituent constants, σp. with the theoretical and experimental parameters related to the strength of hydrogen bond in p-X-TFBA and p-X-ADM molecules also investigated by means of density functional theory calculations. The electronic effects of para-substitutions on the intramolecular hydrogen bond strength were determined by NMR and IR data related to intramolecular hydrogen bond strength, geometry, natural bond orbital results, and topological parameters. These parameters were correlated with the Hammett para-substituent constants, σp. Good linear correlations between σp and the several parameters related to the hydrogen bond strength, in this study were obtained.