Contrary to the popular opinion, it has been found that metallic Ti powder can be directly utilized as dopant precursor to prepare catalytically enhanced NaAlH4 through mechanical milling. As a novel method for preparation of catalytically enhanced NaAlH4, direct metallic Ti-doping possesses practical advantage over the state-of-the-art doping technology: elimination of the inactive by-products and the gas impurities that are highly detrimental to fuel cell operation. A systematic investigation along this new approach was performed under various preparation conditions, including different starting materials, milling atmosphere and milling time. The materials thus prepared under different conditions were found to share some common features, while at the meantime, differ significantly from each other on hydrogen storage performance. A comprehensive understanding of these results provides valuable insight into a series of fundamental questions in catalytically enhanced Ti-NaAlH4 system. Contrary to the popular opinion, it has been found that that metallic Ti powder can be directly utilized as dopant precursor to prepare catalytically enhanced NaAlH4 through mechanical milling. As a novel method for preparation of catalytically enhanced NaAlH4, direct metallic Ti-doping possesses practical advantage over the state-of-the-art doping technology: elimination of the inactive by-products and the gas impurities that are highly detrimental to fuel cell operation. A systematic investigation along this new approach was performed under various preparation conditions, including different starting materials, milling atmosphere and milling time. The materials thus prepared under different conditions were found to share some common features, while at the meantime, differ significantly from each other on hydrogen storage performance. A comprehensive understanding of these results provides valuable insight into a series of fundamental questions in catalytically enhanced Ti-NaAlH4 system.