Photocatalytic degradation of organic pollutants is of great significance for wastewater remediation but is still hindered by the poor catalytic efficiency of the catalysts. Herein, we report a strategy to simultaneously introduce piezocatalysis and to enhance the intrinsic photocatalysis in a single catalyst, which improved the performance for catalytic degradation of methylene blue (MB) significantly. Specifically, piezoelectric BiFeO₃ (BFO) nanotube doped with different contents of Gd and La (Bi_0.9(Gd_xLa_1-x)_0.1FeO₃) were produced by electrospinning. The doping led to a higher concentration of surface oxygen vacancy (OV) in Bi_0.9Gd_0.07La_0.03FeO₃, which effectively increased the piezoelectric field due to the deformation of BFO, and suppressed the recombination of photon-generated electron-hole pairs. The Bi_0.9Gd_0.07La_0.03FeO₃ nanotube showed excellent catalytic performance under simultaneous light irradiation and ultrasonic excitation, giving an extraordinary 95% degradation of MB within 90 min. These findings suggest that the piezoelectric effect combined with defect engineering can enhance the catalytic performance of Bi_0.9Gd_0.07La_0.03FeO₃ nanotube. This could potentially be extended to other catalytic systems for high-performance pollutant treatment.