Understanding the corrosion behavior of rough surface contacts needs the contact interaction of rough surfaces at asperity level. Generally, single asperity-based statistical rough surface contact model is predominating one in exploring contact behavior of rough surfaces. The FEM-based single asperity contact model is being used extensively to explain the elastic, elastic–plastic, and fully plastic behavior of the rough surface contacts. The empirical expressions to calculate the exact transitions (elastic to elastic–plastic and elastic–plastic to fully plastic states) are still incomplete. The earlier FEM-based single asperity contact models didn’t give mathematical expressions to exactly calculate the elastic, elastic–plastic, and fully plastic transition states by accounting the combined effect of material properties. In this way, in the present work, empirical expressions are developed to calculate the exact transitions of elastic, elastic–plastic and fully plastic states by accounting the combined effect of Young’s modulus, material yield strength, and Poisson’s ratio. The empirical expressions to calculate the dimensionless contact load and contact area are developed for elastic, elastic–plastic, and fully plastic states in terms of dimensionless interference, E/Y ratio, and Poisson’s ratio. Further, it is observed that the plasticity index is not a complete parameter to explore the contact behavior of rough surface contacts. In high surface plasticity index case, the material properties influence significantly compared to the low surface plasticity index case. The Poisson’s ratio significantly influences in low E/Y ratio materials in all the surface plasticity index cases.