Thin films of Pb(Mg, Zn)1/3Nb2/3O3 were fabricated by spin coating the Pb-Mg-Zn-Nb-O complex alkoxide sols on(111) Pt-coated MgO (100) planes. It was observed that the content of H2O and the rheological characteristics of sol greatly influenced the orientation of perovskite grains after thin-film formation. A strong preferential orientation of (100)-type planes of the perovskite grains was obtained for the sol aged for 15 days with the molar ratio of H2O to total metal alkoxides=2. As small angle X-ray scattering experiment in the Porod region was performed to correlate the observed preferential orientation with the network structure of precursors at various stage of aging. It was shown that the degree of branching of the Pb-Mg-Zn-Nb-O precursor chain had a direct effect on the preferred oreintation, and weakly branched precursor systems led to highly oriented grains after thin-film formation.