In order to gain insight into the degradation mechanisms associated with ferroelectric thin films, such as fatigue and imprint, an understanding of the defect chemistry and transport properties of the material is needed. In this study several complimentary techniques have been used to either measure or calculate indirectly the various thermodynamic parameters governing defect formation and transport in Pb(Zr1/2Ti1/2)O3, (PZT). By combining the results of DC equilibrium conductivity, thermoelectric power and the sealed cell techniques, “constant composition oxygen activity” and “constant composition conductivity,” values for the oxidation enthalpy (ΔHox), hole trapping energy (EA) and the enthalpy of motion for holes (ΔEA) have been determined to be −0.49 eV, ≤0.9 eV and ≥0.1 eV, respectively. From these results, it is apparent that PZT is an oxygen excessp-type semiconductor in the experimental regime of 500°–700°C and P(O2) ≥ 10−4atm. Furthermore, the results indicate that there is a significant concentration of trapped holes at high temperatures and hole conduction appears to be an activated process (i.e. small polaron conduction).