In　the　present　work,　the　catalytic　effect　of　TiF3　on　the　dehydrogenation　properties　of　LiAlH4　has　been　investigated.　Decomposition　of　LiAlH4　occurs　during　ball　milling　in　the　presence　of　4　mol%　TiF3.　Different　ball　milling　times　have　been　used,　from　0.5　h　to　18　h.　With　ball　milling　time　increasing,　the　crystallite　sizes　of　LiAlH4　get　smaller　(from　69　nm　to　43　nm)　and　the　dehydrogenation　temperature　becomes　lower　(from　80　degrees　C　to　60　degrees　C).　Half　an　hour　ball　milling　makes　the　initial　dehydrogenation　temperature　of　doped　LiAlH4　reduce　to　80　degrees　C,　which　is　70　degrees　C　lower　than　as-received　LiAlH4.　About　5.0　wt.%　H-2　can　be　released　from　TiF3-doped　LiAlH4　after　18　h　ball　milling　in　the　range　of　60　degrees　C-145　degrees　C　(heating　rate　2　degrees　C　min(-1)).　TiF3　probably　reacts　with　LiAlH4　to　form　the　catalyst,　TiAl3.　The　mechanochemical　and　thermochemical　reactions　have　been　clarified.　However,　the　rehydrogenation　of　LiAlH4/Li3AlH6　can　not　be　realized　under　95　bar　H-2　in　the　presence　of　TiF3　because　of　their　thermodynamic　properties.　(C)　2009　Professor　T.　Nejat　Veziroglu.　Published　by　Elsevier　Ltd.　All　rights　reserved.