[en] Low-alkaline cement using pozzolans is under consideration as a possible filling and structural material in geological disposal for long-lived radioactive waste. Silica fume and fly ash are used to develop the low-alkaline cement which is named HFSC, High-volume Fly ash Silica fume Cement. In this study, pore structure and diffusivity of chloride ion in HFSC pastes were investigated in order to understand the fundamental transport properties of ions. HFSC which included different contents of fly ash (40%, 50% and 60%) with silica fume (20%) and ordinary Portland (OPC) cement were prepared. Hardened cement pastes were supplied to pore structure analysis and in-diffusion experiment with NaCl and CaCl₂ solution. Mercury intrusion method (MIP) commonly used and image analysis of backscattered electron microscopy (BSE) for pore in hardened cement paste were performed to investigate the pore structure. The porosity of HFSC was larger than that of OPC measured by MIP. However, pore diameter increasing pore volume of HFSC was smaller than that of OPC. It was observed that lager pores were in HFSC than in OPC from BSE. These large pores in HFSC were originated from cenosphere of FA. The apparent diffusivity of chloride in HFSC with fly ash of 40% showed smallest value in the cement pastes. It was concluded that the smallest diffusion coefficient was caused by a pore of HFSC which had a bended structure and ion exclusion/filtration effect. (author)