The works described a study on the preparation of LiBH4 thin films by means of pulsed laser deposition. The results indicated that crystalline LiBH4 films can be prepared from a LiB target under 70Pa hydrogen atmosphere at ambient temperature. Compared with the former reports of LiBH4, the hydrogen atmosphere and temperature were effectively reduced for the synthetical crystalline LiBH4 films with amorphous Li2B12H12. The mixture was successively dehydrided by two steps in dehydriding reaction, corresponding to the dehydriding amount of approximately 8 and 6 mass%. Compared with the former reports of LiBH4 powder with no catalyzer, the primary dehydriding temperatures of the films was reduced. It will be easy to obtain the hydrogen from LiBH4. This opens up new possibilities to study this important hydrogen storage material. Copyright (c) 2013 John Wiley & Sons, Ltd.