The reaction of aluminum with pure water is an eco-friendly approach to generate hydrogen. The main difficulty associated with this approach is that an oxide or hydroxide protective film around aluminum particles prohibit the hydrogen generation. In this article, a kind of highly activated Al-Ce composite material has been developed via a convenient ball milling method. Typically, Al-13 wt% Ce has a total hydrogen production of 1134 mL/g and a conversion yield of 92.42% within 60 min. The influences of the cerium concentration and ball milling time on the hydrogen production efficiency are discussed based on XPS, XRD, FESEM, and BET techniques. In addition, the hydrogen production efficiency can be improved by adding alkali chloride (NaCl or KCl) to the Al-Ce composite materials.