Antiferroelectric PbZrO3 thin films have been fabricated by a multi-ion-beam sputtering technique at a substrate temperature as low as 415 °C. Single crystal perovskite PbZrO3 films oriented along the a axis could be epitaxially grown on (100)MgO, (100)Pt/MgO substrates using a PbTiO3 buffer layer. The PbZrO3 films achieved high dielectric constants of about 400, which are almost 2.4 times larger than that of bulk PbZrO3. The measurements of D–E hysteresis loops and Curie temperature demonstrated the antiferroelectric to ferroelectric phase transition of PbZrO3 films with a thickness of 1770 Å, while for PbZrO3 films of 875 Å the phase transition could not be clearly observed.