Piezoionics is an emerging mechanical‐electrical energy conversion paradigm that enables self‐powered sensing systems for next‐generation intelligent wearable electronics. However, there are currently no rational design approaches to enhance the stimulus response of piezoionic devices. Here, we present a strategy using crown ether as ion‐selective mobility differential amplifiers for enhancing the pressured‐induced voltage response in ionic polyvinyl alcohol (PVA) hydrogels. The crown ether grafted PVA (PVA‐CE) hydrogel prototype achieves a 30‐fold amplified piezoionic coefficient of 1490 nV Pa−1 within 0 – 1 kPa, compared to 49 nV Pa−1 of the unmodified PVA. The PVA‐CE exhibits an ultra‐low pressure detection limit of 0.2 Pa with a fast response time of 18.1 ms. Leveraging these properties, we further demonstrate a human somatosensory network analogous PVA‐CE piezoionic skin using arrayed pressure sensing. These capabilities hold great promise for emerging healthcare applications such as synthetic biology, soft robotics, and beyond.
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