The TMN 4 moieties have demonstrated significant catalytic activity for oxygen evolution/ reduction reaction (OER/ORR) in carbon-based support materials. Modifying the coordination number and species in the TMN 4 moieties has proven to be an effective approach to regulate their catalytic activity. In this research, by incorporating different triphenylene ligands, we have successfully constructed TMA 2B 2 (TM=Co, Rh, Ir; A/B=N, O, S, Se) moieties with varying coordination environments within 2D metal organic frameworks (MOFs). These moieties serve as an effective model to elucidate the structure-property relationship of two-dimensional 2D-MOFs in OER/ORR. Our findings confirm that alterations in the coordination environment can finely tune the d-band electron distribution of the TM within the TMA 2B 2 unit, particularly activating the d yz and d z2 orbitals of O 2, thereby influencing the interactions between TM and key intermediates. We discovered that the regulatory effect of the coordination environment is closely linked to the electronegativity of the coordinating atoms, which led us to establish reliable descriptors such as φ 1, φ 2, and φ 3 to elucidate the impact of coordination environments on the performance of OER/ORR. This work provides profound insights into the structure-activity relationship, contributing to the advancement of efficient bifunctional electrocatalysts for OER and ORR.