We synthesized methylpiperidine-functionalized graphene oxide (MP-GO) by introducing 4-amino-1-methylpiperidine into reactive epoxy and/or carboxylic acid groups on pristine GO. Then, we applied the MP-GO as a curing catalyst for polyimide (PI) nanocomposites. The MP-GO was found to be an effective base-catalysts for the thermal conversion of polyamic acid (PAA) precursor to PI. Interestingly, when 3 wt% of MP-GO was added to the PI matrix, the complete imidization of nanocomposites was achieved at a temperature lower than 200 degrees C. In addition, the PI/MP-GO nanocomposite films exhibited reinforcement of the oxygen barrier properties which were even better than those of pristine PI, due to the excellent dispersion state of MP-GO and the favorable noncovalent interaction between MP-GO and the PI matrix. Comparison to pristine PI, the oxygen permeability of nanocomposite films that contained only 1 wt% of MP-GO loading was significantly decreased, by about 80%. Furthermore, all the PI/MP-GO nanocomposites exhibited high thermal stability.