AbstractAdvanced conductive hydrogels demonstrate substantial potential for wearable devices. Nevertheless, the transformative advance in soft electronics raises harsh requirements on the hydrogel candidates, such as rapid and on‐site fabrication, mechanical flexibility, high sensitivity, and wide use temperature. Here, this problem is overcome by incorporating a dual catalytic system based on lignin‐modified MXene‐Fe3+ into commercial hydrogels. This system 1) can form a composite hydrogel in a time scale of min at ambient condition without the supply of external energy, 2) incorporates multiple enhanced strategies into polymer chains, and 3) constructs well‐organized hybrid conductive network. The fabricated hydrogel displays an improved and balanced overall performance, including high ductility (2139%), moderate electrical conductivity, and strong temperature tolerance (−70–50 °C). Combined with the great merits of above performance, the hydrogel‐based sensor with good sensing (maximum GF: 2.8), stable repeatability (200% for 200 cycles), and wide work window of 0%–947%, thereby disclosing promising application in physiological movements, such as motion recognition and breathing state detection. Sensationally, even in complex or harsh surroundings, the sensors also produce stable and reliable signal output. Together, the strategy provides a new mentality of designing hydrogel materials for booming and advanced wearable electronics.