One challenge facing the development of air electrodes for Zn–air batteries (ZABs) is the embedment of active sites into carbon, which requires cracks and blends between powder and membrane and results in low energy efficiency during manufacturing and utilization. Herein, a surface phosphorization‐monolithic strategy is proposed to embed CoO nanoparticles into paulownia carbon plate (P–CoO@PWC) as monolithic electrodes. Benefiting from the retention of natural transport channels, P–CoO@PWC‐2 is conducive to the construction of three‐phase interface structure for efficient mass transfer and high electrical conductivity. The electrode exhibits remarkable catalytic activities for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with a small overpotential gap (E_OER − E_ORR = 0.68 V). Density functional theory calculations reveal that the incorporation of P on P–CoO@PWC‐2 surface adjusts the electronic structure to promote the dissociation of water and the activation of oxygen, thus inducing catalytic activity. The monolithic P–CoO@PWC‐2 electrode for quasi‐solid‐state or aqueous ZABs has excellent specific power, low charge–discharge voltage gap (0.83 V), and long‐term cycling stability (over 700 cycles). This work serves as a new avenue for transforming abundant biomass into high‐value energy‐related engineering products.