The introduction of porous hierarchical microstructures effectively improves the sensitivity of flexible capacitive pressure sensors. However, it is still difficult to achieve porous hierarchical microstructures for pressure sensors through inexpensive, efficient, and simple preparation methods. Herein, a hemispherical array with porous hierarchical microstructure was prepared on polydimethylsiloxane (PDMS) substrate by using a simple one‐step microwave curing process with glucose as a porogen. Furthermore, the flexible electrode based on the PDMS substrate was combined with an ionic liquid polymeric gel membrane to obtain a flexible capacitive pressure sensor. Thanks to the deformability of porous hierarchical microstructure and the double dielectric layer effect of ionic liquid polymeric gel membrane, the sensor displays an ultra‐high sensitivity of 131.21 kPa‐1 within the pressure range of 0‐1 kPa. Meanwhile, the sensor has short response time, excellent dynamic loading stability, as well as excellent long‐term stability (>3000 cycles). In application testing, the sensor effectively monitored various physiological activities like pulse, breathe, speech, and swallowing, demonstrating its good prospects in the field of health electronics. Most importantly, the proposed microwave curing method can realize the preparation of porous hierarchical structure on flexible substrate through a one‐step process, which offers a fresh way for the economical, green, and efficient preparation of high‐sensitivity capacitive pressure sensors.A one‐step microwave curing method using glucose as porogen was proposed for preparing porous hierarchical microstructures on PDMS substrate. A highly sensitive flexible piezocapacitive sensor based on porous hierarchical microstructure and an ionic liquid polymeric gel membrane was realized. The piezocapacitive sensor exhibited an ultrahigh sensitivity of 131.21 kPa‐1 and excellent stability over 3000 cycles.This article is protected by copyright. All rights reserved.