Hydrogen storage properties of Ti-doped nanosized (~20 nm) NaAlH(4) supported on carbon nanofibers were affected by the stage at which Ti was introduced. When Ti was deposited first followed by NaAlH(4), sorption properties were superior to the case where NaAlH(4) was deposited first followed by NaAlH(4). This was the result of both a smaller NaAlH(4) particle size and the more extensive catalytic action of Ti in the former material.