High iodine containing oxides are of interest as biocidal components in energetic applications requiring fast exothermic reactions with metallic fuels. Aerosol techniques offer a convenient route and potentially direct route for preparation of small particles with high purity, and are a method proven to be amenable and economical to scale-up. Here, we demonstrate the synthesis of various iodine oxide/iodic acid microparticles by a direct one-step aerosol method from iodic acid. By varying temperature and humidity, we produced near phase pure δ-HIO3, HI3O8, and I2O5 as determined by X-ray diffraction. δ-HIO3, a previously unknown phase, was confirmed in this work. In addition, scanning electron microscopy was used to examine the morphology and size of those prepared iodine oxide/iodic acid particles and the results show that all particles have an irregularly spherical shape. Thermogravimetric/differential scanning calorimetry measurement results show that HIO3 dehydrates endothermically to HI3O8, and then to I2O. I2O5 decomposes to I2 and O2.