Abstract Triboelectric nanogenerator (TENG) as an environmental energy recovery and harvesting technology has attracts much attention. However, the improvement of TENG's output performance becomes one of the core issues. And the modification of triboelectric materials may be an effective approach. Here, two metal–organic framework (MOF) materials namely TIFSIX‐2‐Cu‐i and Cu(Qc) 2 are synthesized, and the influence of different organic ligands on the electromechanical conversion of TENG is investigated by starting from the intrinsic structure of MOFs. With the polydimethylsiloxane (PDMS)@TIFSIX‐2‐Cu‐I and PDMS@Cu(Qc) 2 triboelectric layer, the electrical output of the TENG increases by 4.5 times and 3 times, respectively. Meanwhile, a double dielectric layer composite structure is proposed to further improve the performance of TENG. Accordingly, the MOF‐TENG with a double dielectric layer shows a maximum power density of 0.12 mW cm −2 , which is 6.3 times than that of the original TENG. Based on the designed energy management circuit, the MOF‐TENG exhibits good energy supply capability which can sustainably power small electronics just by harvesting human mechanical energy. This work proposes a new strategy to improve the performance of TENG and may promote the development of self‐powered electronics or systems.