Positron annihilation techniques have been applied to characterize vacancy-related defects in ferroelectric thin film structures. Variable energy positron beam measurements were carried out on doped and undoped Pb(Zr,Ti)O3 (PZT) samples subjected to different post-deposition cool down and anneal conditions. The PZT was deposited by sol-gel with either with platinum or RuO2 electrodes, or by laser ablation with La0.5Sr0.5CoO3 electrodes. The RuO2 and La0.5Sr0.5CoO3 electrode samples showed a smaller S-parameter compared to those deposited with Pt electrodes consistent with an improved PZT layer quality. For laser ablated samples cooled in a reducing ambient an increase in S-parameter for both the PZT and La0.5Sr0.5CoO3 layers was observed indicating an increase in neutral or negatively charged open-volume defects.