The pore structure (i.e. total pore volume, surface area and pore-size distribution curves) was measured using mercury porosimetry and nitrogen sorption. Hydrated portland cement (type I) of water-cement (w/c) ratios 0.3, 0.4 and 0.6 by weight was analyzed at three degrees of hydration (i.e., 30%, 50% and 80%; 70% for the 0.3 w/c system) corresponding to low, intermediate and high levels of hydration. The effect of curing temperature (3°, 23°, and 43°C) on pore structure was also studied. The two techniques were evaluated as well on porous Vycor glass, which has a narrow pore size distribution in the size range accessible to both. Results obtained by both techniques on porous Vycor glass agreed well. However neither technique can be used alone to study the entire pore structure in well-hydrated cement due to the wide range in pore sizes and the presence of micropores. Due to the unstable pore structure in cement a specimen treatment procedure such as methanol replacement, combined with volume-thickness (V-t) analysis, is necessary in order to measure the micropores. At low hydration values the pore structure can be estimated by mercury intrusion porosimetry (MIP). At higher hydration values, however, this technique underestimates total pore volume and surface area due to the presence of micropores which MIP cannot determine. In the pore size range of overlap, higher pore volumes were obtained with MIP. Nitrogen V-t analysis shows that micropores are more pronounced with lower w/c ratios. This finding is consistent with pore size distribution curves obtained by MIP. For a given w/c ratio and degree of hydration the total pore volume measured by MIP was found to be independent of curing temperature in the temperature range studied. At any w/c ratio, capillary porosity is controlled by degree of hydration alone.