An Al-Ga-InSn4-InBi quinary alloy was prepared by a simple smelting and casting method. The phase components and microstructures of the quinary alloy were investigated by means of XRD and SEM with EDX. Two different intermetallic compounds of InBi and InSn4 were simultaneously found in the alloy. Al-Ga-In3Sn and Al-Ga-InSn4 quaternary alloys were prepared in the same way for comparison purpose. The reactions of alloys with water were performed at different water temperatures ranging from 30 to 60 °C. Compared with quaternary alloys, Al-Ga-InSn4-InBi not only can react with water continuously and completely, but also exhibit a relatively more stable hydrogen production rate. Owning to the controllable and everlasting features, the Al-Ga-InSn4-InBi quinary alloy could be more suitable in the field of proton exchange membrane fuel cell (PEMFC) as a fuel provider. Moreover, the reaction of Al with other low melting point metals were measured by DSC. Based on DSC analysis and other results, an activation mechanism was supposed.