The occurrence of water in natural opaline silicas has been studied by differential thermal analysis, thermogravimetric analysis, infra‐red analysis and nuclear magnetic resonance. The results show that in the “crystalline” opals studied, some 90 per cent or more of the total water is physically adsorbed whereas in “amorphous” opals, at least 20 per cent but perhaps much more of the total water is held as hydroxyl groups chemically bonded to the silica surface. The rate of water loss on heating is also different, being chiefly controlled by the pore structure in “crystalline” opals but to a significant extent by the surface structure in “amorphous”.