Understanding and characterizing the relationship between the electrical resistivity and the major influencing factors of the concrete have been all the time a topical research in relation to structural durability. This paper reports an experimental study on the influences of water and chloride contents, and porosity on the electrical resistivity of the Portland cement concrete. The results indicate that the electrical resistivity has a strong correlation with the water and chloride contents in concrete. A new characteristic model has been proposed to represent the correlation. The proposed model has been implemented into a numerical modelling case study of cathodic protection for reinforced concrete structure in saline environment.