Important pore structure parameters related to mechanical properties and durability of cement-based materials can be determined by techniques such as scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), and low temperature calorimetry (LTC). The methods provide information on porosity characteristics as pore volume, pore thresholds and/or pore size distribution in different size ranges and do therefore to a large extent supplement each other. Pastes of w/b=0.4 with 0%, 40% or 70% slag by volume were cured saturated at 20ºC for up to two years. The porosity was characterized by LTC, MIP, and SEM. Higher volume of pores was obtained by MIP compared to results obtained using LTC and SEM. Measured porosity was correlated with predicted porosity using information on the density and degree of hydration of the cement and slag. Porosity estimation showed best agreement with the porosity data measured by MIP. The use of slag showed the same trend for all tests: a higher total volume of pores, but a lower threshold pore size when compared with Portland cement paste. The findings illustrate the importance of measuring not only pore volume but also threshold pore sizes when characterizing porosity of cement-based materials with different binder compositions.