An open tubular capillary column, for high-speed micro liquid chromatography made of a glass tube of the inner diameter not more than 0.10 mm, having the net inside capacity not less than 0.5 .mu.l, the inner surface of which hollow glass tube being chemically bonded, in order to provide a stationary phase there, with at least one silane or its derivative such as octadecylsilane to form a polymeric layer. This invention includes the manufacturing method of such a column.