A hexagonal perovskite BaNiO3 with unusually high-valence nickel(iv) was synthesized under atmospheric and low-temperature conditions by an ethylenediamine-derived wet-chemical route. Secondary phases disappeared with increase in the pH value, and the single-phase BaNiO3 was successfully synthesized at pH 10. The specific surface area was ∼32 m(2) g(-1), which is significantly enhanced compared to the BaNiO3 (0.3 m(2) g(-1)) synthesized by flux-mediated crystal growth. The BaNiO3 was used as an oxygen-evolution reaction (OER) catalyst, and the specific mass activity was ∼5 times higher than that of the BaNiO3 synthesized by flux-mediated crystal growth. As a result, the ethylenediamine-derived sol-gel synthesis could be a simple technique to prepare crystalline compounds such as perovskites and spinels, with unusually high-valence transition metals.