A highly {111}-oriented metal-organic CVD Pb(Zr,Ti)O3 (PZT) is successfully developed using IrOx/Ir instead of Ir as the bottom electrode. The {111} PZT orientation strongly depends on the IrOx thickness and the O2 content of the atmosphere (PO2) during IrO x deposition. During PZT deposition, the Ir surface easily oxidizes and becomes rough, resulting in poor {111} PZT orientation. IrO x prevents Ir surface oxidation and transforms the Ir metal via O2 reduction after the PZT deposition completion. Highly {111}-oriented PZT can be obtained by optimizing the IrO x thickness and PO2 content.