During sorption, the microstructural evolutions of two different cement pastes (with water-to-cement ratios of 0.40 and 0.55) are studied via proton-nuclear-magnetic-resonance relaxometry. The water uptake test is performed for samples dried at 105°C under three different temperatures of 20°C, 40°C, and 60°C for the first twenty-six days of sorption. It is observed that the water went first to the larger pores before migrating to the finest ones. This behavior is accelerated with increasing temperature. The rate of water exchange between fine and large pores is estimated and found to increase with temperature for both studied mixtures. The activation energy corresponding to this water movement is calculated and found to be higher for the lowest water-to-cement ratio, owing its finer microstructure. Finally, the activation energy related to the local water transport in re-distribution from large pores to fine pores is calculated and found to be inferior to the experimental results, which can be explained by the dynamic microstructure not being considered in the classical theories.