Alanates, borohydries, and amides are complex hydrides with high concentration hydrogen that have been actively investigated for materials-based hydrogen storage on-board polymer electrolyte membrane fuel cell (PEMFC) vehicle applications. The major challenge is to release hydrogen at fuel cell working temperature range at fast enough rate without simultaneous desorption of fuel cell poisoning impurities. We review recent progress in hydrogen reaction mechanism and schemes for complex hydride hydrogen storage.