In a hardened concrete, diffusion of oxygen, carbon dioxide, aggressive ions, and moisture from the environment to the concrete takes place through the pore network. It is well known that making dense cement matrix enhances the durability of concrete as well as all the characteristics including strength of concrete. In this paper,9 mix concretes with water to cementitious material ratio (40,45, and $50\%$) and replacement ratio of GGBFS (40 and $60\%$ of cement by weight) were studied on the micro-pore structure by mercury intrusion porosimetry and the accelerated chloride diffusion test by potential difference. From the results the average pore diameter and accelerated chloride diffusivity of concrete were ordered NPC > G4C > G6C. It is concluded that there is a good correlation between the average pore diameter and the chloride diffusivity, and the mineral admixtures has a filling effect, which increases the tortuosity of pore and makes large pores finer, on the pore structure of cement matrix due to the latent hydraulic reaction with hydrates of cement.