Lead zirconate - lead titanate (PZT) materials are commercially important piezoelectric and ferroelectrics in a wide range of applications, such as data storage (dynamic access and ferroelectric random access memories) and sensing and actuating devices. PZT with the morphotropic phase boundary composition offers the highest piezoelectric response and at the present there are no fullydeveloped alternative materials to PZT. The importance of PZT associated with the continuous requirements of device miniaturization, imposes the development of high quality PZT thin films with optimized properties. Concomitantly due to the dependence of the final properties of thin films on the details of the microstructure a thoroughly analysis at the local scale of their microstructure is necessary. Sol-gel method, is one of the Chemical Solution Deposition techniques used to prepare oxide thin films, such as PZT. Starting from a solution, a solid network is progressively formed via inorganic polymerisation reactions. Most metal alkoxides used for sol-gel synthesis are highly reactive towards hydrolysis and condensation. Therefore their chemical reactivity has to be tailored via the chemical modification (or complexation) of metal alkoxides to avoid uncontrolled reactions and precipitation. For PZT sol gel thin film preparation, two chemical routes are frequently used depending on the nature of the molecular precursor, namely methotoxyethanol (MOE) route and diol-route.