An　effective　strategy　of　utilizing　electrospinning　techniques　to　fabricate　MgCl2　catalyzed　ammonia　borane　(AB)　nanofibers　with　a　tunable　fiber　diameter　is　reported.　The　synergistic　effect　obtained　by　combining　nanofibers　and　metallic　catalyst　plays　a　crucial　role　in　the　decomposition　of　MgCl　2-doped　AB　nanofibers,　which　leads　to　significant　improvements　in　dehydrogenation　kinetics　and　complete　suppression　of　unwanted　byproducts.　The　results　of　dehydrogenation　show　that　MgCl2-doped　AB　nanofibers　were　able　to　release　over　10.0　wt　%　pure　H2　below　100　°C　with　favorable　kinetics,　a　significant　advance　over　releases　from　bulk　AB.　Furthermore,　the　dehydrogenation　of　MgCl2-doped　AB　nanofibers　gives　a　weak　exothermic　reaction,　-3.84　kJ　mol-1　H2,　which　is　dramatically　lower　than　that　of　neat　AB　(-21　kJ　mol-1　H2),　which　suggests　that　the　electrospun　sample　is　potentially　more　feasible　to　reverse.　The　findings　in　this　paper　provide　general　guidelines　and　inspiration　for　the　design　and　synthesis　of　novel　nano-fibrous　materials　with　controllable　dimensions　for　hydrogen　storage　applications.　©　The　Royal　Society　of　Chemistry.