Nano-sized Al-substituted alpha-Ni(OH)(2) with high electrochemical performance was synthesized through a chemical co-precipitation method in organic solvent and characterized by means of X-ray diffraction and infrared spectroscopy. Sample's structure stability in concentrated alkaline solution was investigated and the relationship between structure and electrochemical performance was studied. The experimental results show that the mean crystal sizes of samples containing 7.5%,13.2% and 17.2%(molar ratio)Al are 5.4, 6.9 and 11.0 nm respectively. The structure of the sample with 7.5% Al is of the mixture of alpha-Ni(OH)(2) and beta-Ni(OH)(2), whereas the structurers of the samples respectively with 13.2% and 17.2% Al are of pure alpha-Ni(OH)(2). Structure stability increases with Al content increasing due to gradually increased crystallinity and so do its discharge mediate potential and specific electrochemical capacity.