This paper presents an experimental study on the nature of permeation properties and pore structure of concrete surface layers containing fly ash. Concretes containing different dosages of fly ash as a replacement for cement (15% and 30% by weight of total cement materials, respectively) were investigated. Concrete without any fly ash added was also employed as the reference specimen. Laboratory tests were conducted to determine the surface layer properties of concrete including chloride transport, apparent water permeability and pore structure. The results demonstrate that incorporation of fly ash, for the early test period, promotes the chloride ingress at the surface layer of concrete but substituting proportions of fly ash may have little impact on it. With the process of chloride immersion, the chloride concentration at the surface layer of concrete with or without fly ash was found to be nearly the same. In addition, it is suggested that the water permeability at the concrete surface area is closely related to the fly ash contents as well as the chloride exposure time. Pore structure was characterized by means of mercury intrusion porosimetry (MIP) test and the scanning electron microscopy (SEM) images. The modification of pore structure of concrete submersed in distilled water is determined by the pozzolanic reaction of fly ash and the calcium leaching effect. The pozzolanic reaction was more dominant at the immersion time of 180 days while the calcium leaching effect became more evident after 270 days