In spite of the high level of attention paid to multifunctional sensors, the flexible and multifunctionality are still intractable challenges to be tackled. Herein, we design a flexible, hydrophobic and stable multifunctional sensing material by electrostatic spinning of PVDF/ZnWO4@PDA (PZP). The incorporation of ZnWO4@PDA into PVDF nanofibers can act as an effective nucleating agent and photosensitizer, which increases the polar crystalline phase and photovoltaic properties of PVDF. With the synergy of PVDF and ZnWO4@PDA, PZP based piezoelectric sensors offer significantly superior electrical output (28.4 V, 600 nA) and high sensitivity (1.04 V/kPa). Moreover, it is particularly surprising that photoelectric sensor based on PZP textiles has excellent optical properties, as confirmed by the response/recovery time (0.6 s/0.66 s) of simulated sunlight detection. Piezoelectric photoelectric effect exists in PZP textiles, as evidenced by the significant increase in the strain output current of photoelectric sensor when irradiated with sunlight. Furthermore, based on the coupling of piezoelectric effect and triboelectric effect of PZP composite, the contact out nano-triboelectric generator has enhanced the electrical output and electromechanical conversion efficiency. Therefore, this work has successfully prepared multifunctional sensing materials that integrate pressure sensing, audio recognition, underwater communication, optoelectronic detection and triboelectric energy collection, paving a new way for the flexible multifunctional sensors.