This study is the first to demonstrate that ferroelectric R3c LiNbO 3 -type ZnSnO 3 nanowires (NWs), through the piezocatalysis and piezophototronic process, demonstrate a highly efficient hydrogen evolution reaction (HER). The polarization and electric field curves indicate that ZnSnO 3 NWs exhibit typical ferroelectric hysteresis loops. Time-resolved photoluminescence spectra reveal that the relaxation time increases with the increasing concentration of oxygen vacancies. Moderated 3H-ZnSnO 3 NWs (thermally annealed for 3 h in a hydrogen environment) have the longest extended carrier lifetime of approximately 8.3 ns. The piezoelectricity-induced HER, via the piezocatalysis process (without light irradiation), reaches an optimal H 2 -production rate of approximately 3453.1 µmol g −1 h −1 . Through the synergistic piezophototronic process, the HER reaches approximately 6000 µmol g −1 in 7 h. Crucially, the mechanical force-induced spontaneous polarization functions as a carrier separator, driving the electron and hole in opposite directions in ferroelectric ZnSnO 3 NWs; this separation reduces the recombination rate, enhancing the redox process. This theoretical analysis indicates that the photo catalytic and piezocatalytic effects can synergistically enhance piezophototronic performance through capitalizing on well-modulated oxygen vacancies in ferroelectric semiconductors. This study demonstrates the essential role of this synergy in purifying water pollutants and converting water into hydrogen gas through the piezophototronic process.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adfm.201907619. high greenhouse gas emissions, and high energy consumption. Scientists today, being more ecologically conscious, have devised strategies that reduce these negative environmental consequences. Specifically, they have developed catalyst materials that play pivotal roles in the degradation of hazardous pollutants, [1] water splitting, [1][2][3] and energy source conversion. In particular, electrocatalysis [4] and photocatalysis [5] are promising processes for converting solar energy into chemical energy through the irradiation of sunlight. However, challenges remain with respect to improving photoelectrochemical conversion efficiency through doping metal transitions, cocatalysts, [6,7] heterojunction structures, [8,9] and defects states. [10] A sustained effort should be made to accelerate the process of catalyst development using a variety of methods. There has been much recent attention devoted to piezocatalysts, [11][12][13][14] such as MoS 2 , MoSe 2 , and WS 2 , which are made of few-layered 2D materials with unique piezoelectric properties. Specifically, these piezocatalysts have been discovered to have ultrahigh efficiency and to require no light irradiation to convert mechanical energy into chemical energy. [15] Bear this in mind, mechanical energy is naturally available anytime and anywhere. These discoveries have enabled broad engineering applicatio...