Aluminum hydroxides were synthesized by a simple electrolytic reaction of aluminum plates. The aluminum hydroxide, boehmite (AlO(OH)), was predominantly formed in the application of electrical potential at and above 30V, while the mixture of bayerite (Al(OH)_3) and boehmite (AlO(OH)) phases were formed below 20V. The boehmite has a clear fibrous structure controlled on nanometer scale. On the contrary, the bayerite consists of the typical hourglass or semi-hourglass shaped coarse crystals as a result of aggregation of various crystals stacked together. The specific surface area of the boehmite nanofiber was markedly high, approaching at about 302;m2/g.