The corrosion of reinforcement induced by chloride ions is one of the most significant causes of durability deterioration for reinforced concrete (RC) buildings. The concrete material factors, including the water-to-cement ratio (w/c) of concrete, as well as the content, shape, particle grading, and random distribution of coarse aggregate embedded in mortar, have a marked effect on chloride transport performance within concrete. However, comprehensive consideration for the effects of both w/c and coarse aggregate performances on chloride diffusion characteristics in concrete is scarce, especially regarding the chloride diffusion model of concrete. In this paper, an indoor exposure experiment exploring chloride ions intruding into mortar and concrete specimens with w/c = 0.4, 0.5 and 0.6 was carried out, in order to acquire the chloride diffusion parameters for concrete three-phases composites. Based on the numerical algorithm of random generation and placement of two-dimensional random convex polygon coarse aggregate, mesoscopic numerical models for concrete, considering various coarse aggregate contents as well as grading, were established. Using the numerical simulation method of finite element analysis for chloride transport in cement-based materials, which can replace some of the exposure tests, the influences of w/c, coarse aggregate content and grading on chloride diffusion performance in concrete mesoscopic models were systematically probed. According to the Fick’s second law, a chloride diffusion model by the consideration of w/c, volume fraction of coarse aggregate (VFCA), and maximum size of coarse aggregate (MSCA) was developed to assess the chloride concentration profiles in concrete under arbitrary w/c, coarse aggregate content, and coarse aggregate grading conditions. Certainly, the precision accuracy for this proposed chloride diffusion model was validated. The research results can provide theoretical support for chloride erosion behavior and structural durability assessment of concrete with different mix proportions.