HighlightsFreestanding lead-free piezoceramic thin films can be derived via water peeling.Thed33value of the freestanding BCZT thin film reaches 209 pm V−1.The freestanding piezoceramic films obtain versatile application scenarios such as energy harvest and virus detection.Supplementary InformationThe online version contains supplementary material available at 10.1007/s40820-023-01105-6.