In this paper, alternative techniques for the measurement of porosity based upon Gibbs-Thomson equation are reviewed and discussed. The paper focuses on thermoporosimetry trying to demonstrate that it is a valuable tool relevant to sol-gel science. A detailed calibration procedure using sol-gel derived silica gels is presented for acetone. It is then shown that it is possible to predict the behaviour of confined liquids related to a given chemical family. Finally two selected examples illustrate the great potential of this technique for the study of gels networks and cross-linking. Perspectives concerning the study of organic-inorganic hybrids materials are finally given.