The permeability resistance of concrete with ground phosphate slag(GPS) against chloride ion penetration was tested according to ASTM1202 and by nitrogen adsorption method. Test results show that by adding ground phosphate slag to concrete, the chloride diffusion coefficient of concrete decreases, and the permeability resistance of concrete against chloride ion penetration increases with improvement of its pore structure. The pores in concrete are refined and the percentage of the pores with diameter less than 20nm in concrete increases. The improvement of pore structure of the concrete by ground phosphate slag is much better than that by the ground granulated blast furnace slag or fly ash, while the addition is 30 percent. The ability of additive to improve the permeability resistance of concrete against chloride ion penetration is in following order: fly ash > ground phosphate slag > ground granulated blast furnace slag.