Abstract Self‐sustaining mechanical energy harvesting devices are pivotal for developing durable energy‐efficient systems, providing scalable and adaptable solutions to wearable technology. Triboelectric nanogenerators (TENGs) efficaciously convert ambient mechanical energy into usable electrical power to sustainably drive modern electronics. Surface and structural engineering is an avenue to boost TENGs’ energy harvesting through modulating contact interfaces and charge transfer interactions between the constituent layers. This study explores dielectric engineering incorporating an additional transition layer, such as Polyethylene Terephthalate (PET), alongside kapton to store accumulated charges. The surface of molybdenum sulfide (MoS 2 ) is modified with different aromatic carboxylic acids to boost the vertical TENG's performance. The anchoring of aromatic carboxylic acid [4,4′‐Oxybis (Benzoic acid)] modifies the work function and surface charge density of MoS 2 ‐based TENG and enhances the output performance. The output open‐circuit voltage ( V OC ) and short‐circuit current ( I SC ) for “PET‐Kapton@4,4′‐MoS 2 ” TENG increase from 6 to 30 V and 65 to 202nA, respectively. The maximum power density obtained after inserting the transition layer and modifying the MoS 2 surface is 399 mW m − 2 . The “PET‐Kapton@4,4′‐MoS 2 ” TENG can power up to 6 LEDs, run a calculator, and generate International Morse code. A microcontroller unit successfully decodes the Morse code and transmits it wirelessly to a smartphone via Wi‐Fi.