Pb(Zr,Ti)O3 (PZT)-based ferroelectric ceramics exhibit high piezoelectricity, however, their Curie temperature (Tc) values are not so high, i.e., Tc < 400 °C. PZT-based piezoelectric thin films with higher Tc would be beneficial for improved micro actuators, sensors, memories, and piezoelectric micro-electro mechanical systems. In-plane biaxial strained PZT thin films in a laminated composite structure are known to exhibit enhanced Tc; however, the thickness of PZT-based thin films is limited to below a critical thickness typically <50 nm. The Tc of relaxed PZT-based thin films with thicknesses greater than the critical thickness is the same as bulk Tc. However, a sort of relaxed PZT-based single-crystal thin films exhibit extraordinary high Tc, Tc = ∼600 °C. In addition, the films show extremely low dielectric constant, ɛ/ɛo ∼ 100 with high coupling factor, kt ∼ 0.7, and large remnant polarization, Pr ∼ 100 μC/cm2. These exotic properties would result from the single-domain/single-crystal structure. The enhanced Tc is possibly caused by the highly stable interface between the PZT-based thin films and substrates. Their ferroelectric performances are beyond those of conventional PZT. The high-Tc/high-coupling performances are demonstrated, and the possible mechanisms of the high Tc behavior in relaxed PZT-based single-crystal thin films are discussed.