<p>Environmental pollution, especially water pollution caused by the discharge of organic compounds dyes, seriously affects people’s life and health. Catalytic degradation of dyes in wastewater by utilizing natural energy in a non-polluting, low-cost, and efficient manner is a dream goal for researchers. In particular, the development of piezoelectric catalyst materials for the efficient degradation of pollutants has been a top research priority, which is light-independent and can utilize the mechanical energy present in water flow. In this paper, Ag_(I)/BNBT composite nanofibers with different Ag_(I) additions were prepared by electrospinning. The micro-morphology, composition, and piezoelectric catalytic performance of the composite nanofibers were investigated. The results showed that the piezoelectric-catalyzed degradation efficiency and degradation rate of Ag_(I)/BNBT composite nanofibers for RhB dye reached 59.1% and 1.15 × 10⁻² min⁻¹, which were enhanced by 78 and 141.6% compared with that of the matrix fiber BNBT (33.2%, 4.76 × 10⁻³ min⁻¹), respectively. However, over-increasing the ultrasonic power would cause the composite fiber to produce shielding phenomenon and reduce its piezoelectric catalytic efficiency. It was worth noting that the addition of Ag_(I) not only effectively enhanced the piezoelectric output and reduced the charge shielding phenomenon, but also served as a conductive medium to promote charge transfer, which substantially improved the piezoelectric catalytic performance of the material. This indicates that the prepared composite fibers have potential applications in dye wastewater treatment.</p>