Methylammonium lead bromide (CH3NH3PbBr3) (MAPbBr) has been synthesized and then introduced in the poly(vinylidene fluoride) (PVDF) nanofiber made by the process of electrospinning. The β-phase composition, degree of crystallinity as well as mechanical, optical and energy harvesting properties of this composition has been investigated. Increased electroactive phase composition (91%) and dramatic improvement in tensile strength of the PVDF nanofiber mats is found by the addition of MAPbBr. This increase in electroactive phase composition can play a significant role in the enhancement of output power which is a premiere observation. The acoustic nanogenerator (ANG) made from MAPbBr doped PVDF nanofibers (NFs) can also be utilized in energy scavenging from acoustic vibration with a higher degree of acoustic sensitivity (~ 13.8 V Pa−1) and efficiency (58.5%). This suggests that ANG could be a potential tool for power generation in portable electronics. This fact may open up the prospect of using the MAPbBr doped PVDF electrospun nanofibers, with their multifunctional properties such as vibration sensitivity, piezoelectric energy harvesting, green light emission capability (quantum yield ~ 32.6%), for various promising applications in portable electronics, noise detection and security monitoring.