Microcrystalline silicalite-1 was formed on the inner surface of macroporus silica glasses prepared by the sol-gel process. By heating a homogeneous precursor solution at 100°C under a hydrothermal condition, 2–5 μm of plate-like particles of silicalite-1 were deposited. With an increase of mixing time of the precursor solution, the number of silicalite-1 particles increased, accompanied by the relative decrease of the particle size. Depending on the temperature and the duration of the heat-treatment of the macroporous silica, the amount of deposited silicalite-1 varied. Below 1000°C, the amount increased with the heat-treatment temperature, as a result of the competition between the precipitation of silicalite-1 and the dissolution of silica from the macroporous silica glass under a strongly basic condition. On the other hand, above 1000°C the amount of deposited silicalite-1 decreased in accordance with the decrease of the macropore diameter by the heat-treatment, because of the limited transport of the dissolved silicate species through the smaller macropores.