Lithium-oxygen batteries (LOBs) with high energy density are a promising advanced energy storage technology. However, the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in time, resulting in large polarization and battery failure in a short time. Therefore, a self-supporting interconnected nanosheet array network NiCo2O4/MnO2 with a Mott–Schottky heterostructure on titanium paper (TP-NCO/MO) is ingeniously designed as an efficient cathode catalyst material for LOBs. This heterostructure can accelerate electron transfer and influence the charge transfer process during adsorption of intermediate by triggering the interface disturbance at the heterogeneous interface, thus accelerating oxygen reduction and oxygen evolution kinetics and regulating product decomposition, which is expected to solve the above problems. The meticulously designed unique structural advantages enable the TP-NCO/MO cathode catalyst to exhibit an astounding ultra-long cycle life of 800 cycles and an extraordinarily low overpotential of 0.73 V. This study utilizes a simple method to cleverly regulate the morphology of the discharge products by constructing a Mott–Schottky heterostructure, providing important reference for the design of efficient catalysts aimed at optimizing the adsorption of reaction intermediates.