Very intense visible green photoluminescence ͑PL͒ was observed at room temperature in structurally ordered-disordered BaZrO 3 powders. Ab initio calculations, ultraviolet-visible absorption spectroscopy, electron paramagnetic resonance, and PL were performed. Theoretical and experimental results showed that local defects in the cubic structure caused byplay an important role in the formation of hole-electron pairs, giving rise to a charge gradient in the structure which is responsible for PL emission.