In this study, a novel pressurized polyol method is proposed to synthesize aluminum-doped ZnO (AZO) nanoclusters without utilizing additional thermal treatment to avoid the merging of nanoclusters. The size of the AZO nanoclusters range from 100 to 150 nm with a resistivity of 204 Ω cm. The AZO nanoclusters primarily consist of approximately 10-nm nanocrystals that form a spherically clustered morphology. A two-stage growth model has been proposed based on the results of scanning electron microscopy and transmission electron microscopy images, nanocluster sizes, and X-ray diffraction patterns. The primary AZO nanocrystals first nucleate under pressurized conditions and then spontaneously aggregate into larger nanoclusters. Optically, the AZO nanoclusters exhibit a significant decrease in the near-infrared (NIR) transmittance compared to pure ZnO nanoparticles. The NIR blocking efficiency of AZO nanoclusters reached 85%. Moreover, the doping efficiency, resistivity, and NIR transmittance of AZO nanoclusters are influenced by the reaction time in the pressurized polyol solution. On the other hand, the reaction time has no effect on the particle size and crystallinity. An optically transparent coating for the AZO nanoclusters, which consisted of iso-propanol solvent and ultraviolet-curable acrylic binder, was also demonstrated.