We have carried out detailed first-principles studies of the catalytic properties of Ti@Al(100) near-surface alloy. The single Ti atom, (0,2) Ti-Ti pair, and [0,2] Ti doping domain have better catalytic performances. These species doped in the top surface can develop back-bonding interaction with H-2 to catalyze the splitting, which however on the other hand hinder the dissociated H atoms to diffuse. Doped in the subsurface, they can also enhance hydrogen interaction on aluminum to catalyze H-2 splitting. The activation energies are 0.80, 0.68, and 0.48 eV for Ti atom, (0,2) pair, and [0,2] doping domain, respectively. Without Ti-H bond, the dissociated H atom could diffuse away with small energy cost. The structural expansion induced by titanium doping, the lower electronegativity of Ti, and the more valence electrons of Ti may cooperatively facilitate the charge transfer from the above Al atoms to H-2 molecule, accounting for the enhanced splitting properties. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.