 Abstract metal porphyrins or metal thelocyanines-based organic frameworks, POFs, have attracted widespread interest for application in electrocatalysis due to their unique metal and four coordination structure, high conjugated pi-electron system, tunable components, and chemical stability. The key challenges of POFs as high-performance electrocatalysts are the need for rational design for porphyrins-slash-thelocyanines building blocks and an in-depth understanding of structure-activity relationships. Herein, the synthesis methods, the catalytic activity modulation principles, and the electrocatalytic behaviors of 2D-slash-3D POFs are summarized. Notably, detailed pathways are given for modulating the intrinsic activity of the MN4 site by the microenvironments, including central metal ions, substituent groups, and heteroatom dopants. Meanwhile, the topology tuning and hybrid system, which affect the conjugation network or conductivity of POFs, are also considered. Furthermore, the representative electrocatalytic applications of structured POFs in efficient and environmental. This article was authored by Ning Lv, Qian Li, Huang Zhu, and others.