MXene-coated textiles (CFs) demonstrate exceptional conductivity, electromagnetic interference shielding, and thermoregulatory performance, which have become prominent in multifunctional wearable technologies. However, inadequate textile-wettability, shielding-induced secondary pollution, and limited thermoregulation still impede their further multifunctional personal protection under extreme temperatures. Herein, we developed an electroactive hydrogel ink by combining MXene with polyvinylidene fluoride (PVDF) polymeric matrix, and then impregnated it onto the CFs to construct MXene-PVDF-CF (MX-PV-CF). The self-assembled PVDF layer modulates the MXene surface work function by forming a core–shell nanostructure, significantly improving its electro-thermal-magnetic properties. This PVDF-induced low work-function endows MX-PV-CF with remarkable multifunctionalities: 26 dB absorption-dominant electromagnetic radiation protection, high electro-thermal conversion, and a low mid-infrared emissivity (0.65). Mechanistically, the phase transitions of PVDF facilitate efficient heat dissipation, contributing to superior infrared-thermal shielding. Consequently, MX-PV-CF provides excellent extreme temperature protection, maintaining a human-comfortable temperature (10–40 °C) in extremely cold and hot environments. This work enables scalable wearable protection based on MXene-work-function-engineering under extreme temperatures, advancing intelligent protective material technology.