Preparation of potassium niobate from metal alkoxides was investigated. Potassium‐niobium ethoxide, KNb(OC2H5)6, and potassium‐niobium propoxide, KNb(OC3H7)6, were synthesized and subsequently hydrolyzed using several water concentrations (0.75 to 6.0 mol of water/(mol of alkoxide)). Rapid precipitation of potassium‐deficient particles occurred when higher concentrations of water were used. This resulted in the formation of a multiphase material after calcination, as X‐ray diffraction showed the presence of both KNbO3and potassium‐deficient oxide phases(s). Single‐phase KNbO3could be prepared by two methods: (1) hydrolysis of KNb(OC3H7)6/propanol solutions using 1 mol of water (per mole of propoxide) added as a water/propanol solution and (2) hydrolysis of KNb(OC2H5)6/ethanol solutions using 1 mol of water (per mole of ethoxide) added as a water/methanol solution. The latter method provided advantages of low calcination temperature for the formation of single‐phase KNbO3and low weight loss afte