The hydrogen desorption properties of Li2BNH6 were improved by doping with cobalt. With the addition of CoCl2 (7 wt%), more than 8 wt% of hydrogen was released from Li2BNH6 at temperatures below 210°C, which is approximately 90°C lower than that of pristine Li2BNH6. X-ray diffraction, Fourier transform-infrared and Raman characterizations revealed that the dehydrogenation was a stepwise process with the formation of intermediates Li4BN3H10 and LiBH4 and final products of Li3BN2 and LiH. The introduction of Co greatly accelerated the dehydrogenation of Li4BN3H10. X-ray absorption near-edge structure measurements revealed that Co and CoB species formed during ball milling of CoCl2 with LiBH4 and LiNH2, which may function as catalyst in the subsequent dehydrogenation.