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A formula was proved for computing the zeroth-order general Randic index of a hexagonal system to explore the correlation between the zeroth-order general Randic index and the π-electronic energy of a hexagonal system.As a consequence,the extremal hexagonal systems with minimum or maximum zeroth-order general Randic index were completely characterized.Moreover,by using the least-square fit method and regression analysis,a new and close relation was found between the zeroth-order general Randic index and the π-electronic energy of a hexagonal system.So the zerothorder general Randic index is a good measure of the π-electronic energies for benzenoid hydrocarbons.