Abstract: Energy holds a significant position in the national economy and has progressively become a crucial material foundation for the development of human society. Single-atom catalysts (SACs) possess extensive application prospects in the chemical and energy industries. Hence, the development of SACs with desirable high activity, high stability, and low cost holds significant practical implications. In contrast to traditional M-N4 active sites, SACs featuring asymmetric coordination structures have witnessed rapid development in the field of catalysis. This is attributed to their unique electronic and geometric structures, rendering asymmetric coordination a novel and attractive strategy. This article summarizes several typical asymmetric single-atom catalyst structures, namely M-N4-Y (where Y is an axial heteroatom), M-Nx-Y (where Y is a non-metal atom), M-x, and M-M structures.