With the rapid development of wearable electronic skin technology, flexible strain sensors have shown great application prospects in the fields of human motion and physiological signal detection, medical diagnostics, and human-computer interaction owing to their outstanding sensing performance. This paper reports a strain sensor with synergistic conductive network, consisting of stable carbon nanotube dispersion (CNT) layer and brittle MXene layer by dip-coating and electrostatic self-assembly method, and breathable three-dimensional (3D) flexible substrate of thermoplastic polyurethane (TPU) fibrous membrane prepared through electrospinning technology. The MXene/CNT@PDA-TPU (MC@p-TPU) flexible strain sensor had excellent air permeability, wide operating range (0–450 %), high sensitivity (Gauge Factor, GFmax = 8089.7), ultra-low detection limit (0.05 %), rapid response and recovery times (40 ms/60 ms), and excellent cycle stability and durability (10,000 cycles). Given its superior strain sensing capabilities, this sensor can be applied in physiological signals detection, human motion pattern recognition, and driving exoskeleton robots. In addition, MC@p-TPU fibrous membrane also exhibited excellent photothermal conversion performance and can be used as a wearable photo-heater, which has far-reaching application potential in the photothermal therapy of human joint diseases.