Thermally chargeable supercapacitors (TCSCs) are emerging and promising devices that could convert thermal energy spontaneously existing in nature into electricity and then store energy for further utilization. Herein, this work reports on the freestanding 3D Ti3C2Tx MXene‐based TCSC, where lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), poly(ethylene oxide) (PEO), and polyvinylidene fluoride‐hexafluoropropylene (PVDF‐HFP) serve as gel electrolyte. Different from the semiconductor‐based thermoelectric materials, the fabricated Ti3C2Tx TCSC exhibits a high Seebeck coefficient of 78.4 mV K−1. Moreover, when applying a temperature difference (ΔT) of 5.8 K between the cold and hot sides, the Ti3C2Tx TCSC devices provide a stable high voltage of 400.6 mV. The charging/discharging cycles of the Ti3C2Tx TCSC devices upon periodic ΔT of 3.3 and 5.8 K demonstrate their excellent stability. To realize the practical application, the four Ti3C2Tx TCSCs devices connected in series are charged by supplying a ΔT of 5.8 K and used to power a digital timer, demonstrating the possibility and application of the TCSCs in self‐powered integrated electronics.