Nanoporous zirconia with high surface area and crystallinity has a wide range of industrial applications, such as in inorganic exchangers for ion exchange columns, catalyst substrates, and packing material for HPLC. Spherical particles of crystalline nanoporous zirconia are highly desired in various industries due to easy handling of the materials in a fluidized bed. Here, spray drying was adopted to produce spherical nanoporous zirconia powders in both laboratory scale and pilot plant scale. Effect of salts on spray-dried ZrO2 powders and their crystallization behavior was studied. It was found that addition of salts to the zirconia precursors has a huge effect on the crystallization of nanoporous zirconia powders. These results have a great impact on the development of microspheres of nanocrystalline ZrO2 and potentially open up a new opportunity to the low-cost production of porous ceramic microspheres with the salt templating method, in general.