A novel red light‐emitter made of Eu3+ doped self‐poled electroactive poly(vinylidene fluoride–hexafluoropropylene) [P(VDF‐HFP)] hybrid nanocomposite film possesses piezoelectric throughput that is suitable for flexible piezoelectric nanogenerator (PNG) fabrication. We observed that PNG is enabled to generate an open‐circuit voltage of 5 V and 0.35 μA of short‐circuit current under an applied pressure amplitude of ∼10.4 kPa. By simple mechanical energy scavenging, PNG demonstrates an ability to light more than ten blue commercial light emitting diodes instantly, without using an energy‐storage device. Additionally, it successfully charges up capacitors by simple repeating finger touch motion, which indicates its potency as an efficient energy harvesting power source. The high performance of PNG is due to well‐coated Eu3+ with P(VDF‐HFP) in a hybrid nanocomposite so it displays improved dielectric permittivity and energy storage capacity. This flexible composite film also possesses a hypersensitive electronic transition as it responds by an intense red light‐emission confirmed by the CIE 1931 chart. This enables applications in piezo‐photonics as a high‐performance, energy‐saving, flexible solid‐state red light emitter. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2335–2345.