Highly dynamic and stable human electrophysiological monitoring has broad application prospects in intelligent wearable health monitoring, clinical diagnosis of cardiovascular diseases, treatment of nervous system diseases and intelligent human–computer interaction. As a signal interaction bridge between human and the external environment, on-skin electrodes can be attached to the skin surface to monitor and collect various electrophysiological signals in a non-invasive way, making it an ideal platform for highly dynamic and stable electrophysiological monitoring. From the material point of view, the highly dynamic stability of on-skin electrodes depends on the high adhesion and stretchability of the substrate. Therefore, it is an important research direction in the field of flexible intelligent health monitoring to prepare highly adhesive stretchable polymer and construct highly conformal on-skin electrodes that adhere to human skin surface through rational design of polymer structure, so as to realize highly dynamic and stable human electrophysiological monitoring. In this paper, we summarized the recent research progress in our group on the preparation of highly adhesive stretchable polymer and their applications in electrophysiological monitoring with highly dynamic stability, and discussed the opportunities and challenges of highly adhesive stretchable polymer in the next generation of flexible intelligent health monitoring.