Ammonia borane (AB) has attracted tremendous interest for on-board hydrogen storage due to its low molecular weight and high gravimetric hydrogen capacity below a moderate temperature. However, the slow kinetics, irreversibility, and formation of volatile materials (trace borazine and ammonia) limit its practical application. In this paper, a new catalytic strategy involved lithium (Li) catalysis and nanostructure confinement in mesoporous carbon (CMK-3) for the thermal decomposition of AB is developed. AB loaded on the 5% Li/CMK-3 framework releases ∼7 wt % of hydrogen at a very low temperature (around 60 °C) and entirely suppresses borazine and ammonia emissions that are harmful for proton exchange membrane fuel cells. The possible mechanism for enhanced hydrogen release via catalyzed thermal decomposition of AB is discussed.