Differing from graphene with a carbon element component, analogous metallic-graphene two-dimensional layered titanium carbide (2D MXene) provides more opportunities to achieve better surface functionalization. Herein, a thin layered 2D MXene/A-TiO2 composite was prepared by chemical exfoliation and hydrothermal decomposition. The 2D MXene/A-TiO2 composite exhibits high catalytic activity in the adsorption and desorption of hydrogen kinetics for NaAlH4. The critical dehydrogenation temperature of NaAlH4 is similar to 90 degrees C. The first-stage dehydrogenation (similar to 3.0 wt.%) is accomplished in 50 min at 110 degrees C. After the first activated cycle, a constant cycling capacity of 4.7 wt.% is remained for a minimum of five cycles tests. It is found that the excellent catalytic activation should be ascribed to the synergistic effect between homogenous distributed Ti-H and TiC, which are originated from MXene/A-TiO2. The results represent a new step forward in the applications of MXene catalytic dehydrogenation and provide new strategies in the quest for new functional MXene derivatives by insitu modification.