Deposition of chloride ions in the surface layer of concrete is investigated in this study. In real concrete structure, chloride ions from the service environment can penetrate into concrete and deposit in the surface layer, to form the boundary condition for further diffusion towards the interior. The deposit amount of chloride ions in the surface layer is normally a function of time, rather than a constant. In the experimental investigation, concrete specimens with different mix proportions are immersed in NaCl solution with a mass concentration of 5%, to simulate the shallow immersion condition in sea water, and the surface chloride concentrations are measured at different ages. It is found that the surface chloride concentration increases following the increasing immersion durations, and varies from a weight percentage of 0.161%–0.781% in concretes with different mix proportions. The w/c (water-to-cement ratio) influences the surface chloride concentration significantly, and the higher the w/c is, the higher the surface chloride concentration will be, at the same age. However, following the prolonging of immersion duration, the difference in surface chloride concentration induced by w/c becomes smaller and smaller. The incorporation of fly ash leads to higher surface chloride concentration. The phenomena are explained based on pore structure analyses.