Bi(V) compounds of high purity may be synthesized from a variety of Bi(III) compounds in various alkaline hydroxide media. Hypochlorite is a particularly effective oxidant in the synthesis. However, we found that the synthesis of NaBiO3 was a challenge: a small variation in process conditions, such as filtration, reaction time, purification, drying temperature and so on, could lead to decomposition and purity reduction of NaBiO3.