The piezo‐assisted photocatalysis system, which can utilize solar energy and mechanical energy simulteneously, is promising but still challenging in the environmental remediation field. In this work, a novel metal–semiconductor BaTiO₃@ReS₂ Schottky heterostructure is designed and it shows high‐efficiency on piezo‐assisted photocatalytic molecular oxygen activation. By combining experiment and calculation results, the distorted metal‐phase ReS₂ nanosheets are found to be closely anchored on the surface of the BaTiO₃ nanorods, through interfacial ReO covalent bonds. The Schottky heterostructure not only forms electron‐transfer channels but also exhibits enhanced oxygen activation capacity, which are helpful to produce more superoxide radicals. The polarization field induced by the piezoelectric BaTiO₃ can lower the Schottky barrier and thus reduce the transfer resistance of photogenerated electrons directing to the ReS₂. As a result of the synergy effect between the two components, the BaTiO₃@ReS₂ exhibits untrahigh activity for degradation of pollutants with an apparent rate constant of 0.133 min⁻¹ for piezo‐assisted photocatalysis, which is 16.6 and 2.44 times as that of piezocatalysis and photocatalysis, respectively. This performance is higher than most reported BaTiO₃‐based piezo‐assisted photocatalysis systems. This work paves the way for the design of high‐efficiency piezo‐assisted photocatalytic materials for environmental remediation through using green energies in nature.