Irregularly shaped aluminum oxide particles were plasma atomized resulting in narrow size range distribution of spherical nanostructured powders. Cooling rates, on the order of 10 6 to 10 8 K/s, were obtained from the different quenching medias, viz. air, water, and liquid nitrogen. Plasma-engineered powder particles developed nanosize crystallites, while solidification provided insight into the morphological feasibility in refinement of grain size. X-ray diffraction (XRD) methods have been used to quantify the crystallite size obtained with different quenching media. Raman peak shift validated the X-ray analysis in anticipating the grain refinement with increasing cooling rates. Salient structural morphology characteristics and a detailed understanding of spheroidized plasma-sprayed alumina powders were analyzed through scanning electron microscopy (SEM) studies. Formation of nanograins, novel metastable phases, and amorphous structure were endorsed by transmission electron microscopy (TEM) investigations.