Pr3+: La2O3 ceramics was fabricated by conventional ceramics processing and sintered without pressure in H2 atmosphere. The structure and spectroscopic properties of the samples were investigated. The strongest excitation peak is detected at 291 nm, which is corresponding to the 4f−5d absorption band of Pr3+ ion. Pr3+ emits green light in La2O3 ceramics, the major emission peak located at 512 nm belongs to 3P0→3H4 transition. Pr3+:La2O3 owns hexagonal structure and is unstable in air condition, it is easy to absorb water vapor to form La(OH)3.