Oxidation of Si in an alkali solution has attracted much attention to produce hydrogen gas from Si wastes. It was found that hydrogen gas was generated from Si in NaOH and NaF solution with more than 10 times reaction rate than in the NaOH solution. The reaction by-product was a sodium silicate fluoride, Nax+zSiyO2y+x/2Fz solution, and it proved to transform to a glass foam by boiling. The Raman spectrum suggested that the silicon and oxygen atoms in the silicate anions were arranged in a sheet-like structure. This may affect the behavior to form the glass foam.