The synthesis of ZnO comprising different ratios of zinc acetate (ZA) and zinc nitrate (ZN) from the respective zinc precursor solutions was successfully completed via a simple precipitation method. Zinc oxide powders with different mole ratios of ZA/ZN were produced—80/1, 40/1, and 20/1. The crystallinity, microstructure, and optical properties of all produced ZnO powders were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-Vis-NIR spectrophotometry. The average agglomerated particle sizes of ZnO-80/1, ZnO-40/1, and ZnO-20/1 were measured at 655, 640, and 620 nm, respectively, using dynamic light scattering (DLS). The optical properties of ZnO were significantly affected by the extreme ratio differences in the zinc precursors. ZnO-80/1 was found to have a unique coral-sheet structure morphology, which resulted in its superior ability to reflect near-infrared (NIR) radiation compared to ZnO-40/1 and ZnO-20/1. The NIR-shielding performances of ZnO were assessed using a thermal insulation test, where coating with ZnO-80/1 could lower the inner temperature by 5.2 °C compared with the neat glass substrate. Due to the synergistic effects on morphology, ZnO-80/1 exhibited the property of enhanced NIR shielding in curtailing the internal building temperature, which allows for its utilization as an NIR-reflective pigment coating in the construction of building envelopes.