Disclosed herein are a polyimide dope solution composition, a method for preparing a hollow fiber using the composition and a hollow fiber prepared by the method. More specifically, disclosed are a method for preparing a hollow fiber, comprising preparing a polyimide dope solution composition comprising polyhydroxyimide, polythiolimide or polyaminoimide, spinning the composition to prepare a hollow fiber, and thermally rearranging the hollow fiber, and the hollow fiber prepared by the method. In accordance with the method, a hollow fiber made of a high free volume polymer membrane can be prepared by spinning the dope solution composition to prepare a hollow fiber and thermally rearranging the hollow fiber via thermal treatment. The hollow fiber thus prepared exhibits excellent gas permeability and selectivity, thus being suitable for use as a gas separation membrane.