The degradation mechanism of Pb(Zr,Ti)O3 (PZT) under reducing conditions was revealed. In contrast to the significant decrease in the sample weight of SrBi2Ta2O9 due to decomposition, the weight of Pb(Zr,Ti)O3 samples change little during H2-annealing at typical process temperatures. Although no apparent changes were detected by thermogravimetric and x-ray diffraction measurements after annealing, the PZT material did actually change. The main mechanism of the degradation is introduction of oxygen defects into the materials. The oxygen defects produce a donor level within the band gap, and light absorption by this donor level accounts for the change in sample appearance from white to black. Different endurance behaviors of materials against reducing conditions were also found: PbZrO3 decomposes through oxygen dissociation more easily than PbTiO3. Oxygen atoms in PbZrO3 are more weakly bonded to Zr than to Ti in PbTiO3 because of a significant anti-bonding component in the hybridized orbitals.