Calcination and microwave-assisted hydrothermal processing of precipitated zirconium dioxide are compared. Characterization of synthesized products of these two technologies is presented. The infiuence of thermal treatment up to 1200oC on the structural and spectroscopic properties of the so-obtained zirconium dioxide is examined. It was found that initial crystallization of material inhibits the crystal growth up to the 800oC (by means of XRD and TEM techniques), while the material crystallized from amorphous hydroxide precursor at 400oC, exhibits 26 nm sized crystallites already. It was found using the TG technique that the temperature range 100–200oC during the calcination process is equivalent to a microwave hydrothermal process by means of water content. Mass loss is estimated to be about 18%. Based on X-ray investigations it was found that the initial hydroxide precursor is amorphous, however, its luminescence activity suggests the close range ordering in a material.