Electronic skin can detect minute electrical potential changes in the human skin and represent the body's state, which is critical for medical diagnostics and human–computer interface development. On the other hand, sweat has a significant effect on the signal stability, comfort, and safety of electronic skin in a real‐world application. In this study, by modifying the cation and anion of a poly(ionic liquid) (PIL) and employing a spinning process, a PIL‐based multilayer nanofiber membrane (PIL membrane) electronic skin with a dual gradient is created. The PIL electronic skin is moisture‐wicking and breathable due to the hydrophilicity and pore size‐gradients. The intrinsically antimicrobial activities of PILs allow the safe collection of bioelectrical signals from the human body, such as electrocardiography (ECG) and electromyography (EMG). In addition, a robotic hand may be operated in real‐time, and a preliminary human–computer interface can be accomplished by simple processing of the collected EMG signal. This study establishes a novel practical approach for monitoring and using bioelectrical signals in real‐world circumstances via the multifunctional electronic skin.