LAUSR

Piezotronic and plasmonic effects are effective strategies to improve photocatalytic performance. Combining these two effects in one photocatalytic heterostructure is intriguing, but has yet to be reported. Here, a hybrid ternary structure ((silver‐silver sulfide)/barium titanate (Ag‐Ag2S)/BaTiO3) is introduced, where the synergistic exciton–plasmon interaction in Ag‐Ag2S and Ag2S/BaTiO3 heterojunction tuned by piezoelectric polarization can enhance the photon absorption and charge carrier separation to promote photocatalysis efficiency. The exciton–plasmon interaction in Ag‐Ag2S can amplify the plasmon resonance to the semiconductor region and enhance the light absorption of Ag2S. The piezoelectric polarization can tune the band structure of BaTiO3 and then change the heterojunction between Ag2S/BaTiO3 from Type I (i.e., straddling energy band alignments between BaTiO3 and Ag2S) to Type II (i.e., Z‐scheme system between BaTiO3 and Ag2S with a staggered energy band alignment), which can accelerate the separation of electron‐hole pairs. Using this hybrid material, a high methyl orange (MO) degradation rate up to 90% within 30 min is obtained, which is 20% higher than that of Ag/BaTiO3. The demonstrated hybrid material based on the synergistic piezotronic effect and exciton–plasmon interaction shows great promise in pollutant treatment with high efficiency.