In this paper we report on the optical and scintillation properties of Cs2LiYCl6 : Ce3+ and Cs2LiYCl6 : Pr3+ crystals. Crystals of Cs2LiYCl6 doped with different Ce3+ and Pr3+ concentrations were grown and studied under optical, X-ray, gamma ray, and thermal neutron excitation. These scintillators exhibit core-valence and self-trapped exciton luminescence in addition to fast emission from Ce3+ and Pr3+. Efficient thermal neutron detection was observed for both scintillators. The position of the neutron peak in the pulse height spectra was found at about 5 times the channel number of the position of the Cs-137 662 keV gamma peak.