Self-powered wearable piezoelectric sensing devices demand flexibility and high voltage electrical properties to meet personalized health and safety management needs. Aiming at the characteristics of piezoceramics with high piezoelectricity and low flexibility, this study designs a high-performance piezoelectric sensor based on multi-phase barium titanate (BTO) flexible piezoceramic film, namely multi-phase BTO sensor. The substrate-less self-supported multi-phase BTO films had excellent flexibility and could be bent 180° at a thickness of 33 μm, and exhibited good bending fatigue resistance in 1 × 104 bending cycles at a thickness of 5 μm. The prepared multi-phase BTO sensor could maintain good piezoelectric stability after 1.2 × 104 piezoelectric cycle tests. Based on the flexibility, high piezoelectricity, wearability, portability and battery-free self-powered characteristics of this sensor, the developed smart mask could monitor the respiratory signals of different frequencies and amplitudes in real time. In addition, by mounting the sensor on the hand or shoulder, different gestures and arm movements could also be detected. In summary, the multi-phase BTO sensor developed in this paper is expected to develop convenient and efficient wearable sensing devices for physiological health and behavioral activity monitoring applications.