Highly flexible and compliant textile-based electrodes are of considerable interest for the next generation of wearable devices. Engineering interconnected electron transport channels in the insulating textile substrate without any detriment to its intrinsic porous structure, flexibility, and stability generally is a great challenge in developing the high-performance devices. Herein, a strategy to prepare a highly conductive textile by electrostatic self-assembly between positively charged polyester fabric modified with polyethyleneimine (PEI) and negatively charged titanium carbide MXene flakes is presented. The densified, horizontally aligned MXene flakes are painted on the fabric fibers with a low mass loading of 0.8 mg cm−2. They not only form intergral layers of conductive skin, which can be easily charged/discharged at 10 V s−1, but also create numerous active sites for further introducing functional electrochemical materials due to the surface chemistry of the MXene. As a proof-of-concept application, the conductive textile is combined with conformally coated polypyrrole (PPy) and used as a supercapacitor electrode, which has demonstrated large areal capacitance, high rate performance, and outstanding cycling stability without compromising its mechanical endurance. These features suggest the great potential of the as-prepared electrodes and open up a new avenue for the development of a new generation of textile electrode for the smart textile industry.