Fluorine-containing polyimide (FPI) with hydroxyl groups is synthesized from 4,4'-(hexafluoro isopropylidene) diphthalic anhydride (6FDA), 2,2-his (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), and 4,4'-diaminodiphenyl ether (ODA) via high temperature polycondensation. Thereafter, alkynyl groups are introduced into FPI. During the preparation of the composite membrane, alkynyl groups on FPI react with azido methyl of 4,4'-bis(azido methyl) biphenyl via click chemistry and form semi-interpenetrating polymer network (semi-IPN) structure within the composite membranes. The mechanical properties, thermal behavior, water uptake, swelling ratio, proton conductivity, oxidative stability, as well as the performance in single cell operation are investigated. Compared to pure perfluorosulfonic acid (PFSA) polymer membrane, the composite membranes based on semi-IPN of FPI and PFSA exhibit improved mechanical properties, excellent thermal and dimensional stabilities, and suitable proton conductivity. The tensile strength of the composite membranes ranges from 28.0 to 67.0 MPa. With increasing FPI content in the membranes, the dimensional stability of the composite membranes increases. The composite membranes have the proton conductivity from 4.3 x 10(-2) S.cm(-1) to 1.0 x 10(-1) S.cm-1 at 100 C and also have good performances as proton exchange membrane (PEM) in single cell at 80 (C) 2014 Elsevier Ltd. All rights reserved.