Continuous real-time monitoring of air quality is of great significance in the realms of environmental monitoring, personal safety, and healthcare. Recently, flexible gas sensors have gained great popularity for their potential to be integrated into various smart wearable electronics and display devices. However, the development of gas sensors with superior sensitivity, breathability, and stretchability remains a challenge. Here, a new high porosity thermoplastic polyurethane (HP-TPU) foam was reported for gas sensors, which exhibited large three-dimensional network structures and excellent mechanical properties. The HP-TPU foam was achieved by using a simple steam-induced method, which was suitable for mass production. The unique structure endowed this foam with 77.5% porosity, 260% strain ability, and 0.45 MPa Young's modulus, which improved 35, 31, and 80%, respectively, compared to previously reported traditional TPU foam (T-TPU) prepared by the drying method. In addition, the foam presented high gas permeability (312 g/m −2 , 24 h) and excellent stability, and it remained undamaged even after 2000 cycles at 70% strain. The sensing material was coated on a PET flexible interdigital electrode and sandwiched between two HP-TPU foam layers for a gas sensitivity test. Due to the easy diffusion of gas between the pores and contact with the sensing materials, the HP-TPU foam exhibited a significant reduction of 85% in average response time and 46% in average recovery time, compared to the T-TPU foam. A wearable sensing device, comprising sensing, data processing, and wireless transmission modules, was successfully developed to enable outdoor testing and achieved a detection range at the ppb level. Finally, the cytotoxicity test results confirmed that this flexible gas sensor did not harm human health. These results proved that this HP-TPU foam was an ideal matrix for the flexible gas sensor, exhibiting great application potential in the fields of seamless human-machine integration.