This paper reports the results of an investigation of chloride ion penetration and diffusion for high performance concrete. Concrete was prepared incorporating pulverised fuel ash (PFA) and silica fume (SF) with various water-binder ratios. Chloride ion penetration was measured at various ages using rapid chloride permeability test in accordance with ASTM C1202-91. Based on experimentally obtained results, isoresponse contours for chloride permeability were developed showing the interactive and optimized effect between the various parameters investigated. Diffusion coefficient of concrete was determined applying Fick’s law of diffusion. The results show that the inclusion of PFA and SF reduced both chloride permeability and chloride concentration of concrete. It was found that rapid chloride permeability values were consistent with diffusion coefficient of concrete.