Pb(Mg1/3Nb2/3)O-3 (PMN) alkoxide precursor solutions were synthesized and used to prepare thin layers on TiO2/Pt/TiO2/SiO2/Si substrates by spin coating. Many parameters like homogeneity of the solution and appropriate processing must be controlled to minimize the pyrochlore formation. Optimization of the processing allowed highly (111)-oriented thin films to be obtained. Dielectric measurements and TEM investigations were performed and showed that PMN thin films exhibit relaxer behavior.