Medium-ring systems, which constitute a class of structurally intriguing and biologically important molecules, are present in many natural products and pharmaceuticals. However, the construction of these skeletons tends to be difficult because of the torsional strain of the medium-sized ring, and control of the selectivity is also challenging in these flexible skeletons. Electrocyclization is one of the most straightforward methods to construct medium-sized rings and this process typically proceeds in a stereospecific manner, resulting in the stereo-controlled formation of two neighboring stereocenters. At present, there are few studies on 8π electrocyclization, mainly focusing on the synthesis of small molecules, while the applications in the synthesis of functional materials and biological contexts are rare. This feature article highlights recent advances, from 2000 to 2022, in the 8π electrocyclization reaction. This study is organized into four sections based on the size/composition of the target ring, including the synthesis of aza-seven-membered, cycloheptene, cyclooctene and bicyclo[4,2,0]octane frameworks. We expect that this feature article will provide beneficial guidance for the selective construction of medium-ring skeletons.