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Real‐time monitoring of respiration plays a very important role in human health assessment, especially in monitoring and analyzing respiration during exercise and sleep. However, traditional humidity sensors still have problems in flexibility, sensitivity, and durability, so there is an urgent need to develop humidity sensors with high sensitivity, stretchability, and environmental resistance as respiratory monitoring applications. Here, based on the double network hydrogel structure of polyvinyl alcohol and polyacrylamide, a highly sensitive, highly stretchable, and environmentally stable organic hydrogel humidity sensor has been manufactured by using the synergistic effect of lithium chloride and MXene. The hydrogel humidity sensor shows rapid response in the humidity range of 40–85% RH, and has a high sensitivity of −103.4%/% RH. In addition, it exhibits more than 3000% mechanical strain and excellent environmental resistance, which is attributed to the chemical cross‐linking in the hydrogel network and the synergistic effect of multiple hydroxyl groups in glycerol forming rich hydrogen bonds with water and polymer chains. The hydrogel humidity sensor is used for real‐time monitoring of breathing and sleep processes. This work provides a new strategy for preparing high‐performance, extensibility, and environmental stability hydrogel‐based sensors for respiratory monitoring. [ABSTRACT FROM AUTHOR]

Environmentally friendly crosslinked polymer networks feature degradable covalent or non‐covalent bonds, with many of them manifesting dynamic characteristics. These attributes enable convenient degradation, facile reprocessibility, and self‐healing capabilities. However, the inherent instability of these crosslinking bonds often compromises the mechanical properties of polymer networks, limiting their practical applications. In this context, environmentally friendly dual‐crosslinking polymer networks (denoted EF‐DCPNs) have emerged as promising alternatives to address this challenge. These materials effectively balance the need for high mechanical properties with the ability to degrade, recycle, and/or self‐heal. Despite their promising potential, investigations into EF‐DCPNs remain in their nascent stages, and several gaps and limitations persist. This Review provides a comprehensive overview of the synthesis, properties, and applications of recent progress in EF‐DCPNs. Firstly, synthetic routes to a rich variety of EF‐DCPNs possessing two distinct types of dynamic bonds (i.e. imine, disulfide, ester, hydrogen bond, coordination bond, and other bonds) are introduced. Subsequently, complex structure‐ and dynamic nature‐dependent mechanical, thermal, and electrical properties of EF‐DCPNs are discussed, followed by their exemplary applications in electronics and biotechnology. Finally, future research directions in this rapidly evolving field are outlined. [ABSTRACT FROM AUTHOR]