Abstract: The dependence of the directly bonded coupling constants ¹J on some atomic and structural parameters (e.g. atomic order, electronegativity and length of bond etc.) has been investigated in small molecules (ions) It was found that there was a homologous series linear relationship between the proportional coefficient k of the calculated formula and the sum ∑Z' of the effective electronic number of individual atoms in molecules This relationship can be used to the estimation of coupling constants. The calculated result of 46 coupling constants in 34 compouds shows that there is a better agreement between the calculated and the experimental results only with few exceptions.