Zinc oxide, as a widely used material in optics, electronics, and medicine, requires a complete overview of different conditions for facile and easily reproducible syntheses. Two types of optimization of ZnO hydrothermal preparation from zinc acetate and sodium hydroxide solution are presented, which allowed for obtaining miscellaneous morphologies of materials. The first was a temperature-controlled synthesis from 100 to 200 °C, using citric acid as a capping agent. The formation of hexagonal rods at the lowest temperature was evidenced, which agglomerated to flower-like structures at 110 and 120 °C. It was followed by transformation to flake-like roses at 160 °C, up to disordered structures composed of nanosized plates (>180 °C). The transformations were generated through a temperature change, which had an impact on the diffusion effect of hydroxide and citrate complexes. The second optimization was the hydrothermal synthesis free of organic additives and it included only a pH variation from 7.5 to 13.5. It was found that by utilizing a slow-dropping process and varying amounts of NaOH solutions, it is possible to obtain well-formed hexagonal pellets at pH 8.0-8.5. Strongly basic conditions of pH 11.0 and 13.5 impeded superstructure formations, giving small elongated particles of ZnO. All samples were characterized by high phase purity and crystallinity, with a specific surface area of 18-37 m2/g, whereas particle size distribution indicated a predominance of small particles (<1 μm).