A method of manufacturing a hollow fiber in which a spinning solution of cellulose ester dissolved into an organic solvent is extruded from an annular slit, and simultaneously a core liquid is introduced into the inside hollow portion of the extruded spinning solution, the core liquid being selected from the group of hydroxycarboxylic acid, derivative of hydroxycarboxylic acid, monoterpene or these mixture, or consisting of a solution of the above-described compound or mixture.