In this work, new LaSi3N5:Ce3+ phosphors have been synthesized by solid-state reaction. Rietveld refinement of the crystal structure of La1−xCexSi3N5 reveals that Ce atoms substituted for La atoms occupy 4a crystallographic positions. Broad emission and excitation bands observed were attributed to the transitions between the doublet ground state of the 4f1 configuration and the crystal field components of the 5d1 excited state. At 77 K, the centroid and crystal field splitting εcfs of the 5d levels of Ce3+ in LaSi3N5:Ce3+ compounds were valuated at 33.4×103 and 11.3×103 cm−1, respectively. The zero-phonon line and the Stokes shift were measured to be 26.0×103 and 5.0×103 cm−1, respectively.