The geometrical models of 2-(2-Hydroxyphenyl)benzoimidazole with alkali(or alkaline earth) metal ions were fully optimized by using B3LYP density functional theory at the 6-311++G(d, p) level. Results indicate that the cation-π interaction between metal ions and HBI compounds are strong, some of these even reach a chemical bond strength. The energy barrier of the intramolecular proton transfer increased or decreased by Cation-π interaction and injection solvent effects and these show in the relative energies display.