In the era of artificial intelligence and the internet of things, the emergence of flexible MICAtronics, heterostructures made by van der Waals epitaxy on layered mica, has attracted great research interest due to applications in the fields of flexible ferroelectric memory, dielectric capacitors, and others, but less effort has been dedicated to the realization of flexible piezoelectric inorganic films for energy harvesters and sensors. In this work, an all-inorganic transparent Sm-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (Sm:PMN-PT) film has been successfully grown on Mica substrate via a simple one-step sol-gel process. The flexible film shows an ultrahigh piezoelectric coefficient d33 of 380 pm V−1 owing to the enhanced local structural heterogeneity and the weak substrate clamping effect. Simultaneously, superior flexibility is realized without sacrificing its electrical performance, as reflected by withstanding a small radius of curvature of 2 mm and even 103 mechanical bending cycles. Utilizing this Sm:PMN-PT film, the fabricated device exhibits an excellent energy harvesting performance with output voltage of 6 V, current density of 150 μA cm−2, andultrahigh force sensitivity of 5.86 V N−1. Besides, it also possesses a certain temperature resistance and favorable hydrophobicity. In practical applications, it can not only be employed to monitor body motions, including finger pressing, hand tapping, foot stepping, finger/wrist bending, and hand grasping, but also serves as a tactile sensor to record the touch of a finger to unlock a smartphone. This work demonstrates that the flexible PMN-PT based film on Mica substrate has full application potential in mechanical energy harvesting, motion sensing, and human-machine interaction.