A new methodology to decorate the surface of polyimide (PI) fiber with carbon nanotubes (CNTs) has been developed in this study. This surface decoration was carried out through a surface alkali treatment, a carboxylation modification, surface functionalization with acyl chloride groups and then with amino groups, and a surface graft of CNTs onto PI fiber. Fourier-transform infrared and X-ray photoelectron spectroscopic characterizations confirmed that CNTs were chemically grafted onto the surface of PI fiber, and scanning electron microscopic observation demonstrated the fiber surface was uniformly and densely covered with CNTs. The surface energy and wettability of PI fiber were improved in the presence of CNTs on the fiber surface, which made a contribution to enhance the interfacial adhesion of PI fiber with other inorganic matrices when used as a reinforcing fiber. The application of CNTs-decorated PI fiber for the reinforcement of phosphoric acid-based geopolymers was investigated, and the results indicated that the geopolymeric composites gained a noticeable reinforcement. Compared to unreinforced geopolymer, the geopolymeric composites achieved a remarkable increase in compressive strength by 120% and in flexural strength by 283%. Fractography investigation demonstrated that the interaction adhesion between the fibers and matrix was enhanced due to the surface decoration of PI fiber with CNTs, which contributed to an improvement in fracture-energy dissipation by fiber pullout and fiber debonding from the matrix. As a result, a significant reinforcement effect on geopolymeric composites was achieved through a fiber-bridging mechanism. This study provided an effective methodology to improve the interracial bonding force for PI fiber and also proves a highly efficient application of CNTs-decorated PI fiber for the mechanical enhancement of geopolymeric composites. (C) 2017 Elsevier B.V.All rights reserved.