High‐resolution and bright‐ and dark‐field transmission electron microscopy are used to characterize and compare the interface structures and microstructure of PZT/RuO2/SiO2/Si and PZT/Pt/Ti/SiO2/Si ferroelectric thin films, with a view to understanding the improved fatigue characteristics of PZT thin films with RuO2 electrodes. The RuO2/PZT interface consists of a curved pseudoperiodic minimal surface. The interface is chemically sharp with virtually no intermixing of RuO2 and PZT, as evidenced by the atomic resolution images as well as energy dispersive x‐ray analysis. A nanocrystalline pyrochlore phase Pb2ZrTiO7-x, x≠1, was found on the top surface of the PZT layer. The PZT/Pt/Ti/SiO2/Si thin film was well crystallized and showed sharp interfaces throughout. Possible reasons for the improved fatigue characteristics of PZT/RuO2/SiO2/Si thin films are discussed.