Progress in Li-O2 battery (LOB) research is pivotal for achieving the ambitious goal of full electrification of transport. However, difficulties in promptly catalysing the sluggish oxygen kinetics remain the long outstanding challenge hindering the progress in LOB technology. Herein, the groundsel flower-like hierarchical microsphere network of NiCoP/NiCo2O4 (NCP@NCO/Ni) is synthesised in situ grafting on nickel foam as a high-performing oxygen cathode for LOBs. Both oxygen reduction and evolution reactions are kinetically enhanced by the presence of heterogeneous NiCoP and NiCo2O4 promoting surface electron transfer. The assembled LOB cells demonstrate an exceptional lifespan, withstanding over 400 cycles under a very high charge rate of 800 mAg-1 while achieving the highest discharge/ charging capacities of 15710/ 14632 mAh g-1 at 100 mAg-1 with low charging overpotentials, owing to unique catalytic support and fast charge transfer occurred across the interface in the heterostructure. Interestingly, the discharge capacity is only reduced by 10% to 14092 mAh g-1 even after the charge rate increases by 6 times, where the capacities of the pure metal phosphide and metal oxide cathodes fade substantially. The facile decomposition of sheet-like Li₂O₂ well-attached to the cathode surface enhances the cell’s reversibility and performance, overcoming the drawbacks of alternative Li₂O₂ morphologies.