A method for preparation of Ti-doped NaAlH4 with high hydrogen capacity was developed, in which the NaH/Al mixture was mechanically milled with a catalytic amount of KH together with metallic Ti. The addition of KH was found to result in a pronounced improvement in the dehydriding performance of the Na3AlH6/NaH+Al step. As a result, the practical cycling hydrogen capacity has been markedly enhanced from 3.3 wt % for the Ti-doped hydride to 4.7 wt % for KH+Ti co-doped material. Moreover, the pronounced enhancement on hydrogen capacity arising upon adding KH was observed to persist in the following dehydrogenation/hydrogenation cycles. Structural investigation shows that the addition of KH has led to a lattice expansion. Moreover, it was found that the enthalpy change of the Na3AlH6/NaH+Al decomposition step underwent a considerable decrease upon adding KH. Therefore, the observed property improvement may be ascribed to a favorable thermodynamic adjustment arising upon the addition of KH.