For achieving more effective mechanical energy conversion, based on low-cost and flexible polydimethylsiloxane (PDMS) and polyvinylidene fluoride (PVDF) polymer film as triboelectric and piezoelectric function layer respectively, a polymer-based hybrid piezoelectric-triboelectric nanogenerator (PT-NG) with a structure of Al/PVDF/Cu-PDMS/indium tin oxide (ITO)/polyethylene terephthalate (PET) has been demonstrated. The device has realized the simultaneous triboelectric and piezoelectric conversions in one structure. In addition, when PDMS and PVDF are further modified by graphene quantum dot (GQD) and titanium dioxide (TiO2) nanoparticles respectively, both triboelectric and piezoelectric outputs of the modified device are greatly enhanced synchronously. The experimental results have indicated that the increase of triboelectric output is due to the improvement of dielectric properties of PDMS film doped with conductive GQDs as well as the enhancement of the effective contact caused by the change of PDMS surface microstructure. While the promotion of piezoelectric output is mainly attributed to the fact that PVDF film after TiO2 modification induces more polarized β phase with a polarization-free process. Accordingly, the modified device converts mechanical energy into electricity more effectively, which shows a promising prospect in the fields of flexibility display, electronic skin, wearable electronic products and self-powered sensors.