On‐skin electrodes function as an ideal platform for collecting high‐quality electrophysiological (EP) signals due to their unique characteristics, such as stretchability, conformal interfaces with skin, biocompatibility, and wearable comfort. The past decade has witnessed great advancements in performance optimization and function extension of on‐skin electrodes. With continuous development and great promise for practical applications, on‐skin electrodes are playing an increasingly important role in EP monitoring and human–machine interfaces (HMI). In this review, the latest progress in the development of on‐skin electrodes and their integrated system is summarized. Desirable features of on‐skin electrodes are briefly discussed from the perspective of performances. Then, recent advances in the development of electrode materials, followed by the analysis of strategies and methods to enhance adhesion and breathability of on‐skin electrodes are examined. In addition, representative integrated electrode systems and practical applications of on‐skin electrodes in healthcare monitoring and HMI are introduced in detail. It is concluded with the discussion of key challenges and opportunities for on‐skin electrodes and their integrated systems.