In this study, a new, relatively simple fabrication method for forming a mesoporous Al(OH)3 film onAl substrates was demonstrated. This method, i.e., alkali surface modification, was simply comprised of dippingthe substrate in a 5×10-3M NaOH solution at 80oC for one minute and then immersing it in boiling waterfor 30 minutes. After alkali surface modification, a mesoporous Al(OH)3 film was formed on the Al substrate,and its chemical state and crystal structure were confirmed by XPS and TEM. According to the results of theXPS analysis, the flake-like morphology after the alkali surface modification was mainly composed of Al(OH)3,with a small amount of Al2O3. The mesoporous Al(OH)3 layer was composed of three regions: an amorphous-rich region, a region of mixed amorphous and crystal domains, and a crystalline-rich region near the Al(OH)3layer surface. It was confirmed that the stabilization process in the alkali surface modification stronglyinfluenced the crystallization of the mesoporous Al(OH)3 layer.