Self-poled molybdenum disulfide embedded polyvinylidene fluoride (MoS₂@PVDF) hybrid nanocomposite films fabricated by a bar-printing process are demonstrated to improve the output performances of triboelectric nanogenerators (TENGs). Comparative analyses of MoS₂@PVDF films with different MoS₂ concentrations and the synergic effect based on postannealing at different temperatures were examined to increase the triboelectric open-circuit voltage and the short-circuit current (∼200 V and ∼11.8 μA, respectively). A further comprehensive study of the structural and electrical changes that occur on the surfaces of the proposed hybrid nanocomposite films revealed that both MoS₂ incorporation into PVDF and postannealing can individually promote the formation of the β-crystal phase and generate polarity in the PVDF. In addition, MoS₂, which provides triboelectric trap states, was found to play a significant role in improving the charge capture capacity of the nanocomposite film and increasing the potential difference between two electrodes of TENGs. The produced electrical energy of the developed wearable TENGs with excellent operational stability for a long duration was utilized to power a variety of mobile smart gadgets in addition to low-power electronic devices. We believe that this study can provide a simple and effective approach to improving the energy-harvesting capabilities of wearable TENGs based on hybrid nanocomposite films.