Accurate and reliable monitoring of dynamic electrophysiological signals is essential for advancing human health. However, gaps and relative movements between the detection electrodes and human skin can severely interfere the accuracy and stability of acquired bioelectrical signals. Here, an approach to rapidly form a stable bioelectronic interface through an in situ self-catalytic reaction at the interface between an organogel electrode and the epidermal tissue of skin, referred to as the epidermisgel interlocking electrode (EGIE), is proposed. Significantly, the electrode with an interlocking structure exhibits superior interfacial adhesion, excellent epidermal conformability, outstanding mechanical stability, stable electrochemical performance, and good biocompatibility. Accurate and reliable detection of electrocardiogram (ECG) signals during walking, squatting, jogging, and post-sweating, as well as electromyogram (EMG) signals during leg stretching exercises and running activities, is achieved with a signal-to-noise ratio of 21.83 ± 0.12 dB. An EGIE-enabled ECG wear is further developed for multi-parameter physiological monitoring during dynamic human activities, which demonstrates the promising application of the proposed method.