In the solution processing of oxide electronics, the structure of metal-organic precursors in solution and their effect on processability and on the final structure and properties of the oxide have rarely been studied. We have observed that hybrid clusters, having inorganic cores coordinated by organic ligands, are the typical form of metal-organic precursor structures. For insulating ternary LaZrO, improved synthesis of the cluster precursor under solvothermal conditions led to low-temperature deposition of the film at 200 degrees C, as we will report in another paper. In the current paper, we first briefly show that solvothermal synthesis of the precursor resulted in significantly improved insulating properties (e.g., two orders lower leakage current) of high-temperature-annealed films, and then focus on the structural analysis of the cluster precursors and annealed solids and relate the results to the significant improvement of properties by solvothermal treatment of solutions. A change in the cluster core toward structural unification was brought about by solvothermal treatment, resulting in higher uniformity and higher stability of clusters. The final structure of the material maintained the features of the core structure in solution, even after annealing at high temperatures. These results demonstrate the key role played by designing cluster structure in solution.