Composite nanofibers of Eu3+ doped poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP))/graphene are prepared by the electrospinning technique for the fabrication of ultrasensitive wearable piezoelectric nanogenerators (WPNGs) where the post-poling technique is not necessary. It is found that the complete conversion of the piezoelectric β-phase and the improvement of the degree of crystallinity is governed by the incorporation of Eu3+ and graphene sheets into P(VDF-HFP) nanofibers. The flexible nanocomposite fibers are associated with a hypersensitive electronic transition that results in an intense red light emission, and WPNGs also have the capability of detecting external pressure as low as ~23 Pa with a higher degree of acoustic sensitivity, ~11 V Pa-1, than has ever been previously reported. This means that ultrasensitive WPNGs can be utilized to recognize human voices, which suggests they could be a potential tool in the biomedical and national security sectors. The capacitor's ability to charge from abundant environmental vibrations, such as music, wind, body motion, etc, drives WPNGs as a power source for portable electronics. This fact may open up the prospect of using the Eu3+ doped P(VDF-HFP)/graphene composite electrospun nanofibers, with their multifunctional properties such as vibration sensitivity, wearability, red light emission capability and piezoelectric energy harvesting, for various promising applications in portable electronics, health care monitoring, noise detection and security monitoring.