Multifunctional electrocatalysts with high catalytic activity and durability are needed for environmentally clean energy technologies such as water-splitting devices and metal–air batteries. Herein, we investigate a new catalyst, P-3G, consisting of a cation-ordered perovskite (PrBa0.5Sr0.5)0.95Co1.5Fe0.5O5+δ (PBSCF) and 3D porous N-doped graphene (3DNG). This new type of composite electrocatalyst simultaneously exhibited outstanding multifunctional catalytic activities and excellent stabilities for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). A possible mechanism for the synergistic effects between perovskite oxides and 3DNG on ORR, OER and HER was firstly proposed by DFT calculations. The electrocatalytic activity of P-3G appeared to have great potential for a rechargeable Zn–air battery system. The operating voltage differences between the charge and discharge (Δη) of P-3G and Pt/C–IrO2 after 110 cycles were 0.63 V and 0.87 V, respectively, indicating the substantial durability of P-3G. Moreover, a water-splitting device using P-3G efficiently produced H2 and O2 gases at rates of 0.859 μL s−1 and 0.417 μL s−1, respectively. This study highlights extended applications of coupled perovskite oxides/carbon materials as versatile electrocatalysts for ORR, OER, and HER and unveils the cause of synergistic interactions between oxide and carbon by DFT calculation.