Rare earth solution (RES) surface modification and air-oxidation methods were used to improve the interfacial adhesion of the carbon fiber reinforced polyimide (CF/PI) composite. The flexural property of the PI composites reinforced by the carbon fibers treated with different surface modification methods was comparatively investigated. Results showed that the flexural strength of CF/PI composite was improved after RES treatment. The improvement of impact and flexural property of the CF/PI composite was mainly due to the improvement in interfacial adhesion after RES treatment. X-ray photoelectron spectroscopy (XPS) study of carbon fiber surface showed that the oxygen concentration was obviously increased after RES treatment. The increase in the amount of organic functional groups increased the interfacial adhesion between CF and PI matrix.