ORR catalysts to accelerate the reaction but restricted by their scarcity, high cost, and poor durability. [14][15][16] Thus, exploring Pt-free catalysts is exceptionally urgent to replace the precious metal catalyst. [17][18][19][20][21] Single-atom catalysts (SACs) have attracted considerable interest because they offer 100% metal atom utilization and show excellent catalytic behavior compared with traditionally supported nano-particles. Besides, its regulated coordination structure, large specific surface, abundant active sites and intrinsic activity provides its excellent catalytic performance, selectivity, and stability superior to other catalysts. [22][23][24] Transition metal combined with SACs make these catalysts being the promising candidates to replace platinum group metal (PGM) catalysts. Transition-metal single-atom electrocatalysts (M-N-C, M = Fe, Co, Ni, Zn, Cu, Mn.) hold the advantages of maximum atom utilization efficiency and high-efficiency intrinsic activity. [21][22][23][24][25][26][27][28] Among these transition metals, Fe is abundant in the earth which makes the Fe-N-C received extensive attention. Besides, compared with other transition metalbased SACs, experimental results and theoretical calculation have proved that the Fe-N-C structure exhibits the highest ORR performance during the catalytic procedure owns the appropriate adsorption energy of the oxygen-containing intermediates. [29][30][31] In recent decades, massive efforts have devoted to improving the electrocatalytic performance of single-atom Fe-N-C catalysts. [32][33][34][35][36][37][38] Further improving the single-atom Fe-N-C catalyst performance faces a grand challenge of their limit of intrinsic activity and the active site density. To address these issues, a considerable amount of strategy research has focused on enhancing the intrinsic activity by modulating the coordination structure and optimizing the electronic structure of the Fe-N-C catalysts, including doping hetero-atoms (B, P, S, and N), [39][40][41][42][43][44][45] formatting bimetallic active site, [46][47][48] engineering defect structure. [49][50][51] While increasing the active site density, the strategies of pore structure designing and multiple templates show very encouraging progress. [52][53][54][55][56] However, establishing the synergistic correlation between the intrinsic activity and their active density and manifesting the structure-activity relationship is highly appealing yet different. [57] Platinum group metal ( PGM)-free M-N-C catalysts have exhibited dramatic electrocatalytic performance and are considered the most promising candidate of the Pt catalysts in oxygen reduction reaction (ORR). However, the electrocatalytic performance of the M-N-C catalysts is still limited by their inferior intrinsic activity and finite active site density. Regulating the coordination environment and increasing the pore structure of the catalyst is an effective strategy to enhance the electrocatalytic performance of the M-N-C catalysts. In this work, the coordinati...