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To reveal the effects of microwave irradiation on the structure, morphology, and supercapacitor performance of p-phenylenediamine (PPD)-functionalized graphene materials (FG), FG was synthesized by using PPD as a functional modifier with the combination of hydrothermal reflux and microwave irradiation. The results showed that microwave irradiation could realize rapid reduction of functionalized graphene oxide (FGO). With increase of the irradiation time, the structural defects decreased while the sp2 plane domains increased. Moreover, the lamellae began to decompose into small aggregates. Before microwave irradiation treatment, FGO exhibited good supercapacitor performance with superior specific capacitance of 614.2 F g−1 at 0.5 A g−1. However, after microwave irradiation, the supercapacitor performance of FG got worse, and the configuration types of nitrogen atoms in the FG structure changed significantly. These results indicate that microwave irradiation is not conducive to improvement of the supercapacitor performance of FG. [ABSTRACT FROM AUTHOR]