Capability of thermal neutron detection was examined for LiCaAlF 6 (LiCAF) scintillators doped with 3d-transition metal ions. Their radioluminescence spectra were measured with an 241-Am source to simulate 6 Li(n, α) 3 H reaction. The sufficiently intense radioluminescence was observed for the Mn, Co and Cu dopants, while only a weak one was observed for Ti, V, Fe and Ni. A Mn doped LiCAF crystal, which showed the highest radioluminescence intensity, was coupled with a Si avalanche photodiode for the examination of its neutron response. It was confirmed that the average current of the photodiode clearly increased under excitation with 13.5 meV neutron flux.