As potential hydrogen storage mediums, ammonia borane and its derivatives have been paid an increasing attention owing to their higher hydrogen capacities and facile dehydrogenation properties under moderate conditions. In this chapter, we presented extensive studies on thermodynamic tailoring of dehydrogenation of metal amidoboranes, metal borohydride-ammonia borane complexes, and metal amidoborane ammoniates as well as their derivatives, with special focus on the syntheses, crystal structures, and dehydrogenation properties. Finally, future perspective was given toward the practical applications.