Triboelectric nanogenerators (TENGs) are one of the most trending energy harvesting devices because of their efficient and simple mechanism in harvesting mechanical energy from the environment into electricity. Herein, ferroelectric and dielectric bismuth tungstate (Bi2WO6 (BWO)) with a marigold flower‐like structure is prepared via a hydrothermal method, which is embedded in poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP), forming a PVDF‐HFP/BWO composite polymer film (CPF) to fabricate TENGs. Generally, the ferroelectric materials exhibit a large piezoelectric coefficient, high electrostatic dipole moment, and high dielectric constant. The prepared PVDF‐HFP/BWO CPF reveals a high polar crystalline β‐phase which leads to enhanced piezoelectric and ferroelectric properties of the CPF, thus resulting in the increased electrical performance of the fabricated TENG. The electrical output performance of the proposed TENG is systematically investigated by varying the amount of BWO material embedded in the PVDF‐HFP polymer. The fabricated PVDF‐HFP/2.5 wt% BWO CPF‐based TENG device exhibits the highest electrical output performance. Additionally, the robust test of the TENG device is conducted to investigate the electrical performance for long‐term durability and mechanical stability. Finally, the proposed TENG is operated as a self‐powered sensor, harvesting mechanical energy from daily life human activities, and powering various low‐power portable electronics.