The achievement of flexible skin electrodes for dynamic monitoring of biopotential is one of the challenging issues in flexible electronics due to the interference of large acceleration and heavy sweat that influence the stability of skin-electrode interfaces. This work presents materials and techniques to achieve self-healing and shear-stiffening electrodes and an associated flexible system that can be used for multichannel biopotential measurement on the skin. The electrode that is based on a composite of silver (Ag) flakes, Ag nanowires, and polyborosiloxane offers an electrical conductivity of 9.71 × 104 S/m and a rheological characteristic that ensures stable and fully conformal contact with skin and easy removal under different shear rates. The electrode can maintain its conductivity even after being stretched by more than 60% and becomes self-healed after mechanical damage. The combination of the electrodes with a screen-printed multichannel flexible sensor allows stable monitoring of both static and dynamic electromyography signals, leading to the acquisition of high-quality multilead biopotential signals that can be readily extracted to yield gesture recognition results with over 97.42% accuracy. The conductive self-healing materials and flexible sensors may be utilized in various daily biopotential sensing applications, allowing highly stable dynamic measurement to facilitate artificial intelligence-enabled health condition diagnosis and human-computer interface.