Corrosion inhibition properties of some heterocyclic compounds (3-mercapto 1,2,4 triazole, benzotriazole, thiophene, and tetra hydro-thiophene) in Cu/H3PO4 medium were investigated theoretically and experimentally via cluster/polarized continuum and gravimetric approaches. Second-order MOller-Plesset perturbation and density functional theories were applied, and the electronic chemical potential, molecular softness, and extent of charge transfer were determined for inhibitor molecules at the metal/solution interface. Good correlations were observed for both theories between the calculated quantities and experimental data. To reveal the quality of metal-inhibitor interactions, comprehensive analyses were carried out on various active centers of the compounds. It was concluded that the interactions are mostly physical, and the molecules with less electron-inducing effect act more efficiently.