Porous silica ceramics were prepared(with HCI catalyst) using H2O/TEOS molar ratios of 2.6~59.0, with the EtOH/TEOS ratio fixed. After preparing 9 kinds of sol, the followings were investigated; measurement of the gelation time, thermal analyses by TG/DTA, property analyses of the intermediates by FT-IR and X-ray diffractometry with dried samples, analyses of SiO2 polymer by FT-IR, the investigation of specific sur-face area and pore size distribution by N2-adsorption isotherm, and structural change of SiO2 polymer and pore morphology by TEM observation, with samples heat-treated to 50$0^{circ}C$. In the concentrations of in-vestigated compositions and catalyst, gelation time showed a minimum at ca. 11 moles of water per one mole of TEOS, the highest degree of polymerization at ca. 8-18 moles, and the largest specific surface area at ca. 11 moles, which means that the polymerization proceeded fastest at ca. 11 moles of water. In con-clusion, the more water used, the faster the polymerization reaction up to ca. 11 moles, but more than ca. 11 moles of water caused retardation of gelation and resultant reduction of specific surface area.