A new method is described to prepare nano silica porous layer columns by using in-situ sol-gel synthesis technology. By the interaction of ethyl acetate and water glass solution, the nano silica was synthesized on the inner surface of fused silica capillary. The influence of reaction conditions on the morphology surface area, pore volume and pore size was investigated. The experimental results demonstrate that when the mole ratio of ethyl acetate to silica was 0.82, the particle size of the superfine silica powder was in the range of 25-50 nm, the BET specific surface area was 420 m2/g, and the total pore volume was 0.68 cm3/g. The nano silica porous layer on the inner surface of fused silica capillary was formed by bonding reactions through cross-linked polysiloxane chains, and deactivated by 1 g/L KCl. The column shows sufficient selectivity, stable retention performance, proper resistance to water, good reproducibility, and unique activity. The column is suitable for the analysis of chlorofluorocarbons, halohydrocarbons, sulfur compounds, and light hydrocarbons C1-C4.