Intense photoluminescence was observed from mixed-valence Eu-doped nanocrystalline BaAl₂Si₂O₈/LaBO₃ glass ceramics. For preparation in air, the ratio between Eu3+ and Eu2+ luminescence depends on synthesis temperature. XRD, TEM and IR absorption spectra were employed to characterize the crystallization process and structural properties of the precursor glass and corresponding glass ceramics. When annealed at 950 °C, the material exhibited photoluminescence more than ten times stronger than was found in its glassy state. Spectroscopic data indicate that during such a heat treatment, even in air, a significant part of the Eu3+ ions is reduced to Eu2+. Lifetime of the ⁵D₀ state of Eu3+ increases with increasing heat treatment temperature. Eu3+ species are largely incorporated on La3+ sites in LaBO₃ crystallites whereas Eu2+ locates on Ba2+ sites in the hexacelsian phase. A mechanism for the internal reduction of Eu3+ to Eu2+ is proposed. Spectroscopic properties of the material suggest application in additive luminescent light generation.