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Flexible thin‐film thermoelectric devices (TEDs) can generate electricity from the heat emitted by the human body, which holds great promise for use in energy supply and biomonitoring technologies. The p‐type Sb2Te3 hexagon nanosheets are prepared by the hydrothermal synthesis method and compounded with Ti3C2Tx to make composite films, and the results show that the Ti3C2Tx content has a significant impact on the thermoelectric properties of the composite films. When the Ti3C2Tx content is 2 wt%, the power factor of the composite film reaches ≈59 µW m−1 K−2. Due to the outstanding electrical conductivity, high specific surface area, and excellent flexibility of Ti3C2Tx, the composite films also exhibit excellent thermoelectric and mechanical properties. Moreover, the small addition of Ti3C2Tx has a negligible effect on the phase composition of Sb2Te3 films. The TED consists of seven legs with an output voltage of 45 mV at ΔT = 30 K. The potential of highly flexible thin film TEDs for wearable energy collecting and sensing is great.