Conductive multi-walled carbon nanotubes (MWCNTs) as well as piezoelectric zinc oxide (ZnO) nanoparticles are frequently used as a single additive and dispersed in polyvinylidene fluoride (PVDF) solutions for the fabrication of piezoelectric composite films. In this study, MWCNT/ZnO binary dispersions are used as spinning liquids to fabricate composite nanofibrous films by electrospinning. Binary additives are conducive to increasing the crystallinity, piezoelectric voltage coefficient, and consequent piezoelectricity of as-spun films owing to the stretch-enhanced polarization of the electrospinning process under an applied electric field. PCZ–1.5 film (10 wt. % PVDF/0.1 wt. % MWCNTs/1.5 wt. % ZnO nanoparticles) contains the maximum β-phase content of 79.0% and the highest crystallinity of 87.9% in nanofibers. A sensor using a PCZ–1.5 film as a functional layer generates an open-circuit voltage of 10 V as it is subjected to impact loads with an amplitude of 6 mm at 10 Hz. The piezoelectric sensor reaches a power density of 0.33 μW/cm2 and a force sensitivity of 582 mV/N. In addition, the sensor is successfully applied to test irregular motions of a bending finger and stepping foot. The result indicates that electrospun PVDF/MWCNT/ZnO nanofibrous films are suitable for wearable devices.