The classical electrical double layer (EDL) theory explains the interaction between ions and charged soil colloidal particles, playing an importance role in the bioavailability and toxicity of ions in soils, which are of agricultural and environmental concerns. A new approach based on extrapolating measurements of suspension Wien effect is suggested to determine the adsorbed ions distribution in the different compartments of the EDL. The new approach was applied to assess Zn²⁺ distribution in the EDL of Zn-saturated soil colloids. The results showed that more than 84% of Zn²⁺ was adsorbed via chemical interactions and located in the inner Helmholtz plane layer. The remaining Zn²⁺ fraction was electrically adsorbed and distributed in the outer Helmholtz plane layer (0.3% to 2.1%) and in the Gouy-Chapman diffuse layer (7.4% to 15.0%). Independently, the results of linear combination fitting (LCF) of extended X-ray absorption fine structure (EXAFS) spectra indicated that the contents of outer-sphere Zn in paddy soil I and boggy soil were consistent with the proportions of Zn²⁺ electrostatically interacting with the soil colloids based on the extrapolation of the suspension Wien effect method, while the contents of outer-sphere Zn in paddy soil II, yellow cinnamon soil and yellow brown soil was overestimated by the EXAFS method. The approach proposed in this paper to assess specific and electrostatic adsorption deepens our understanding of metal sorption processes in soils and reinforces the adequacy of the Grahame-Stern-Gouy-Chapman EDL model to describe the ion distribution in the solid-water interface.