Graphene possesses unprecedented physical and chemical properties and has been thought to be ideal filler for reinforcing fibers' mechanical properties. However, graphene is difficultly dispersed in polymer which severely restrict to prepare high-strength and high-modulus composites. In this work, we report an effective method to fabricate a kind of organ-soluble polyimide (PI)/graphene composite fiber using in situ polymerization. Graphene oxide (GO) is modified by 4,4'-diaminodiphenyl ether (ODA) to obtain the GO-ODA nanosheets which exhibit excellent dispersibility and compatibility with the organ-soluble PI matrix. WAXD results show that these 2D nanosheets have a significant influence on the crystallization, aggregation or assembly behaviors of the polymer chains. The PI/graphene composite fiber containing 0.8 wt% of GO-ODA presents a tensile strength of 2.5 GPa (1.6 times higher than the pure PI fiber), and tensile modulus of 126 GPa (223% raises compared with pure PI fiber). Furthermore, the incorporation of graphene significantly improves the glass transition temperature and thermal stability of the composite fibers. Thanks to the excellent hydrophobic properties of graphene, the hydrophobic behavior of the composite fibers is greatly improved. This effective approach shows a potential application in fabricating multifunctional polymer-based composite fibers. (C) 2013 Elsevier Ltd. All rights reserved.