The aim of this work was to examine the microstructural changes of CEM I standardised cement mortar caused by accelerated carbonation (20% CO₂ concentration) using porosity accessible to water and nitrogen adsorption. The conflicted results obtained by these two techniques showed the differences in porous domains explored, while the pore size distributions calculated from nitrogen adsorption provided evolution of the micro and meso pores during carbonation. The porosity accessible to water showed changes in all three porous domains: macro, meso and micro pores. This is because of difference in the molecular sizes between water and nitrogen molecules. Although these two techniques are different, they help to complementarily evaluate the effects of carbonation. The results also indicated the influence of type of cement on microstructural evolutions and the correlation between variations of mesopores volume and specific surface area. Changes in microstructure induce changes in macroscopic properties that we also examined such as the solid phase volume using helium pycnometry, the gas permeability, the thermal conductivity, the thermal diffusivity, and the longitudinal and transverse ultrasonic velocities.