Electrochemical sensors are critical to artificial intelligence by virtue of capability of mimicking human skin to report sensing signals. But their practical applications are restricted by low sensitivity and limited cycling stability, which result from piezoionic mechanism with insufficient sensing response. Here, we report a highly sensitive ultrastable sensor based on proton-coupled electron transfer, which is different from piezoionic mechanism. The sensor gives a high sensing signal output of 117 mV, which is 16 times higher than that of counterpart device (7 mV). It delivers excellent working stability with performance retention as high as 99.13% over 10 000 bending cycles in air, exceeding that of the best-known sensors reported previously. The flexible sensor displays high sensitivity in detecting real-time signals of human activities with large and subtle deformations, including wrist bending, moving speed, pulse wave and voice vibration. Smart functions, such as braille language and handwriting recognitions, are demonstrated for artificial intelligence.