Purchased piezoelectric ceramic particles have a high surface activity, a low dielectric constant, and a low ferroelectric performance. The piezoelectric activity of piezoelectric ceramic particles was further improved by improving the interface bonding state between the piezoelectric ceramic particles and the polymer matrix. In this study, the piezoelectric ceramic particles were treated at a high temperature under nitrogen protection. Crystal forms of the piezoelectric ceramic particles were analyzed via X-ray diffraction (XRD) and scanning electron microscopy (SEM) technologies. The dielectric and piezoelectric properties of the piezoelectric film, which were influenced by the heat treatment process, were the focus of this study. The heat treatment temperature of the piezoelectric ceramic particles was determined, and piezoelectric film sensors were prepared. The applied research of the piezoelectric film sensors was performed via a cantilever beam experiment. The results showed that the heat treatment resulted in the decomposition of strong groups at the piezoelectric ceramic particle surface, the surface activity of the particles decreased, the interface compatibility of the piezoelectric ceramic particles and the polymer matrix was enhanced, the reasonable heat treatment temperature was 1200 ℃, and the piezoelectric film sensors that were used for the real-time monitoring of structures were effective.