Penetration and diffusion of chloride ions in concrete can lead to the corrosion of steel bar and shorten the service life of concrete structures. Phosphoaluminate cement (PAC) is a new cementitious material which has many special properties compared to Portland cement (PC). In the study, chloride ion diffusion in PAC concrete was tested with RCM method. The phase composition and morphology of hydration products, pore volume of hardened paste cured for 28d were analyzed with X-ray diffraction (XRD) and mercury intrusion porosimetry (MIP). The results show that chloride ion diffusion coefficient of PAC concrete is much lower than that of Portland cement concrete under the same test conditions. The hydration products of PAC are main micro-crystalline phase and gel of phosphate and/or phophoaluminate, which formed a dense microstructure. There is no calcium hydroxide produced in the PAC hydration system. In hardened PAC paste, chloride ions might replace the atom group [OH] - and [PO4]3- of hydrates and become stable compounds. The resistance to chloride ion diffusion of PAC concrete will increase with the hydration age, because its microstructure becomes denser with the hydration age increasing.