Changes of the relative water content of the pore liquid in lithium conducting silica sol/gel monoliths were studied. The initial composition of the sols was TMOS:H2O:HCl:LiX:MeOH:HPS = 1: 20:5 x 10(-4):0.2:3:10(-5) (LiX = LiNO3, LiCl or LiBr). The measurements were made by spectrofluorimetry with pyranine as a photoprobe. Initial changes of water content are due to the hydrolysis of TMOS molecules. Low rates of condensation lead to an almost constant level of water content over long periods of time, following the hydrolysis. Pin-holing of the Parafilm seals produces faster changes of water content. These changes are ascribed to the effect of preferential methanol evaporation and entrapment of some liquid inside closed or very narrow pores of the gels.