Jiawei Gu, Qiongle Peng, Xuanqi Zhong, Yi Zheng, Zhiqiang Ma, Xiaoxian Song, Ruihuan Zhang, Bao Liu, Yanhu Zhang, Zhengbao Yang
Abstract The pursuit of multifunctional sensors has intensified due to their potential for integrated, efficient operation. However, realizing a flexible material that combines simplicity in the fabrication process with high performance and multifunctionality remains a formidable challenge. In this study, a multi‐interface heterostructured nanofiber membrane composed of Polyvinylidene fluoride (PVDF), HfO 2 , and nano‐copper is fabricated, leveraging the synergistic interplay of piezoelectric and piezo‐phototronic effects for flexible, self‐powered sensing. The incorporation of hafnium oxide (HfO 2 ) and nano‐Cu enhances the crystallinity of the piezoelectric β ‐phase and improves the dielectric properties, substantially boosting electromechanical performance. The resultant piezoelectric sensor achieves an output voltage of 15V and maintains stability over 5000 cycles at 5 Hz, enabling precise detection of human motions. Meanwhile, the PVDF/HfO 2 ‐based photodetector exhibits broadband sensitivity (from near‐UV to near‐IR), high photoresponsivity (5.67 mA W −1 ), high detectivity (4.14×10 11 Jones), and rapid response (600 µs rising, 53 µs falling). Critically, the device demonstrates a 28.6% current enhancement under simultaneous light and pressure, highlighting a strong piezo‐phototronic effect. This work presents a multifunctional fiber film for dual‐mode sensing (pressure & light), with promising applications in wearable electronics and aerospace systems. Its straightforward fabrication and high performance offer a viable pathway toward next‐generation, flexible, self‐powered sensors.