The electrocatalytic applications of traditional polyimide film and carbon nanomaterials are hindered due to a shortage of three-dimensional hierarchical conductivity and porous structure. Herein, a novel polyimide-based electrode based on a highly efficient palladium nanocatalyst embellished three-dimensional reduced graphene oxide/polyimide foam (Pd/3D RGO@PI foam, signed PRP) toward H 2 O 2 electroreduction was designed and prepared through thermal foaming procedure, followed by facile dip-drying method and electrodeposition. As expected, such a binder-free, 3D hierarchical structure PRP electrode presented high catalytic property, good stability, as well as low activation energy toward H 2 O 2 electroreduction during the electrochemical measurement period. The PRP electrode showed a reduction current density of 810 mA•cm −2 at −0.2 V (vs Ag/AgCl) in 2.0 mol•L −1 H 2 SO 4 and 2.0 mol•L −1 H 2 O 2 . Moreover, the PRP electrode also illustrated good reproducibility and repeatability. Reproducibility presented almost 95.8% of the initial current density after 1000 cycles test. Also, the activation energy of H 2 O 2 electroreduction on 3D PRP electrode was 21.624 kJ•mol −1 . Benefiting from the 3D hierarchical structure and efficient catalyst, the PRP electrode exhibited excellent electrocatalytic performance and was considered to be a potential candidate material for fuel cells.