Hybrid piezoelectric/triboelectric nanogenerators combine the merits of piezoelectric nanogenerators (PENGs) and triboelectric nanogenerators (TENGs), possessing enhanced electrical output and sensitivity. However, the structures of the majority of hybrid nanogenerators are rather complex in integrating both functions, limiting their practical application in wearable electronics. Herein, we propose to construct a piezoelectric/triboelectric hybrid nanogenerator (PT-NG) with a simple structure based on a composite film to simultaneously achieve the coupling of piezoelectric charge generation and triboelectrification with improved energy conversion efficiency. The composite film consists of electrospun PVDF nanofibers embedded in the surface of the PDMS film, which not only forms a rough nanomorphology on the surface of PDMS but also provides structural protection to the PVDF nanofibers by PDMS during compressive deformation. The results have shown that the PT-NG can generate much higher electrical outputs than individual TENG and PENG devices. The PT-NG devices exhibit a high level of mechanical-to-electrical energy conversion efficiency with superior performance in charging capacitors and functioning as self-powered wearable sensors for the detection of different signals from finger movement, the recognition of various gestures, and the monitoring of respiration. More importantly, the composite device possesses an impressive structure durability, maintaining its layered structure over 5000 testing cycles without noticing any obvious damage on the nanofibers or detachment between the layers. Our results have demonstrated that the combining of piezoelectric nanofibers and triboelectric substrate is an efficient way to fabricate highly efficient energy harvesting devices for intelligent identification and health monitoring.