Crack‐free Pb(Zr,Ti)O3(PZT) thin films with preferred orientation were prepared successfully on MgO (100), SrTiO3(100), and Pt/Ti/SiO2/Si substrates from metal alkoxide solutions. Calcination of precursor films in a H2O─‐O2gas mixture was found to be effective not only for low‐temperature crystallization of perovskite PZT, but also for obtaining the preferred orientation of PZT films. Single‐phase PZT films with high preferred orientation were synthesized on MgO (100) and Pt/Ti/SiO2/Si substrates at 550° and 600°C for 2 h, respectively. The PZT film on the Pt/Ti/SiO2/Si substrate showed a permittivity of 520, tan δ of 0.03, a remanent polarization of 24 μC/cm2, and a coercive fiel