Using hydrogen as a transportation fuel has been attracting considerable interest due to zero carbon emissions from vehicles. Storing hydrogen compactly, safely and affordably remains a major scientific and technological challenge in on-board applications. Over the past decade, significant efforts have been made in developing solid-state hydrogen storage techniques. Among the chemical storage materials, ammonia borane is one most promising candidate because it has a high hydrogen density of 19.6 wt% and it is a non-flammable and non-explosive crystalline compound at ambient conditions. Hydrogen can be extracted from ammonia borane via thermolysis, hydrolysis, hydrothermolysis, and methanolysis. This review covers various approaches and prospects of facilitating thermolysis, along with a brief discussion of the nature of ammonia borane and the regeneration of spent fuel.