A novel approach to the rational fabrication of smart and functional metal oxide particulate thin films and coatings is demonstrated on the growth of ZnO nanowires and oriented nanorod arrays. The synthesis involves a template-less and surfactant-free aqueous method, which enables the generation of, at large-scale, low-cost, and moderate temperatures, advanced metal oxide thin films with controlled complexity. The strategy consists of monitoring of the nucleation, growth, and aging processes by means of chemical and electrostatic control of the interfacial free energy. It enables the control of the size of nano-, mess-, and microcrystallites, their surface morphology, orientations onto various substrates, and crystal structures.