Dual valence Eu-doped transparent glass-ceramics containing LuPO4 nanocrystals were fabricated by melt-quenching technique in air atmosphere. Their luminescent properties were systematically investigated by excitation, emission spectra, and decay lifetime measurements. The prominent Stark splitting, low forced electric-dipole 5D0–7F2 transition and long decay lifetimes of Eu3+ emission for glass-ceramics reveal the incorporation of Eu3+ into LuPO4 nanocrystals. The enhanced Eu2+ emission and reduction mechanism of Eu3+ to Eu2+ after crystallization are discussed briefly. Our results indicate that transparent LuPO4 glass-ceramics may find applications in photonics.