Hydrogels are ideal building blocks to fabricate the next generation of electrodes for acquiring high‐quality physiological electrical signals, for example, electroencephalography (EEG). However, collection of EEG signals still suffers from electrode deformation, sweating, extensive body motion and vibration, and environmental interference. Herein, polyvinyl alcohol and polyvinylpyrrolidone are selected to prepare a hydrogel network with tissue‐like modulus and excellent flexibility. Additionally, polydopamine nanoparticles, obtained by polydopamine peroxidation, are integrated into the hydrogel to endow them with higher transparency, higher self‐adhesion, and lower impedance. Consequently, a multichannel and wirelessly operated hydrogel electrode can establish a conformal and stable interface with tissue and illustrate high channel uniformity, low interfacial contact impedance, low power noise, long‐term stability, and a tolerance to sweat and motion. Furthermore, the hydrogel electrode shows the unprecedented ability to classify the recorded high‐quality prefrontal EEG signals into seven‐category sustained attention with high accuracy (91.5%), having great potential applications in the assessment of human consciousness and in multifunctional diagnoses.