Turning the built-in electric field by modulating the morphology and microstructure of ferroelectric materials is considered a viable approach to enhancing the piezo-photocatalytic activity of the ferroelectric/oxide semiconductor heterojunctions. Here, hydrothermally synthesized single-crystalline BaTiO3 nanoparticles are employed to construct BaTiO3@TiO2 hybrid nanofibers by sol-gel assisted electrospinning of TiO2 nanofibers and annealing. Because of the obvious enhancement of the synergetic piezo-photocatalytic effect under both ultrasonic and ultraviolet (UV) light irradiation, the piezo-photocatalytic degradation rate constant (k) of BaTiO3@TiO2 hybrid nanofibers on methyl orange (MO) reaches 14.84 × 10-2 min-1, which is approximately seven fold that for piezocatalysis and six fold that for photocatalysis. Moreover, BaTiO3@TiO2 core-shell nanoparticles are also synthesized for comparison purposes to assess the influence of microstructure on the piezo-photocatalysis by a wet-chemical coating of TiO2 on BaTiO3 nanoparticles. Such a high piezo-photocatalytic activity is attributed to the enhancement of the piezotronic effect by the single-crystalline ferroelectric nanoparticles and the nanoconfinement effect caused by the one-dimensional boundary of nanofibers with high specific surface areas. The mechanically induced uniform local built-in electric fields originated from the single-crystalline ferroelectric nanoparticles can enhance the separation of photogenerated electron and hole pairs and promote the formation of free hydroxyl radicals, resulting in a strong piezotronic effect boosted photochemical degradation of organic dye. This work introduces the single-crystalline ferroelectrics to construct ferroelectric/oxide semiconductor heterojunctions, and the enhanced local piezotronic effect uniformly strengthens the photochemical reactivity, which offers a new option to design high-efficiency piezo-photocatalysts for pollutant treatment.