Thermoporometry was employed to monitor the mesopore evolution in wet, drying and heat-treatment stages of monolithic macro/mesoporous silica with SBA-15 like structure. Direct comparison of mesopores in wet state was only possible with the samples extracted with sulfuric acid. In good agreement with the preceding study, the sulfuric acid not only removed the surfactant but also modified the silica gel network into that with reduced amount of micropores and increased stability against the drying stress. Thermoporometry revealed that the structural evolution takes place completely in the wet condition, which accompanies a decrease in the thickness of non-freezable water.