Owing to the exhaustion of non-renewable resources such as fossil fuels and the increasing seriousness of environmental pollution, it is urgent to find alternative energy. Hydrogen energy has been extensively studied for its cleanness and sustainability. An important issue for the utilization of hydrogen energy is the hydrogen storage and transportation. The complex hydrogen storage materials with Al–H bond have been regarded as promising materials for hydrogen storage due to its large hydrogen storage capacity. This paper mainly introduced the new research progress of the composition, preparation, crystal structure and hydrogen storage properties of several kinds of complex hydrogen storage materials with Al–H bond, such as alkali metal, alkaline-earth metal and some other metal-aluminum hydrides.