Scintillation and luminescence characteristics of Rb2LiYBr6 doped with 0.1%, 0.5%, 1%, and 5%?Ce3+ are presented. Under optical and x-ray excitation, Ce3+ doublet emission is observed at 385 and 420 nm. Rb2LiYBr6:0.5%?Ce3+ shows very high thermal neutron scintillation light output of 83?000 photons/neutron. An excellent neutron peak resolution of 3.6% (full width at half maximum over peak position) is observed for the 4.8 MeV neutron-reaction products energy response in Rb2LiYBr6:0.1%?Ce3+. This peak shows up at 3.6 MeV ?-equivalent energy and therefore it gives an ?/? ratio of 0.74. The combination of a large fraction of neutron absorption in natural i?(62%), a sharp neutron response peak, high light yield, and large ?/? ratio makes Rb2LiYBr6:Ce3+ an efficient scintillator for thermal neutron detection.