The pore parameters of cement pastes blended with volcanic rock at the curing age of 1, 28 and 90 d were determined by a mercury intrusion porosimetry. The pore structure of the pastes was characterized through the analysis of porosity, average pore diameter, the most probable pore aperture, pore size distribution, as well as total pore volume. For the improvement of mechanical property and durability of cement-based material, the correlation of the formed pore structure with hydration time and replacement level of volcanic rock for cement was revealed. The results indicate that volcanic rock can diminish porosity and reduce pore size in cement paste when curing time prolongs, which is particularly prominent with replacement level of less than 20% in late period. The more harmful pores(i.e., capillary pore) are gradually transformed into harmless pore(i.e., gel pores or micropore), even fully filled and disappeared when hydration products increase. The pore structure of the cement paste is thus refined. The beneficial effect of volcanic rock on the pore structure of cement paste could enhance the mechanical property and durability of cement-based material.