The hydrogen storage properties of 2NaBH4 +MgH2 system were studied. It was found that the presence of MgH2 could destabilize the decomposition of NaBH4, decreasing the dehydrogenation temperature about 40℃ compared with the pure NaBH4. It is believed that the formation of MgB2 upon dehydrogenation stabilizes the dehydrogenated state and, thereby, destabilizes the NaBH4. For the desorption the following two-step reaction was observed: 2NaBH4 +MgH2→2NaBH4 +Mg+H2→2NaH +MgB2 +4H2. Furthermore, various catalysts such as TiF3, TiO2, Zr, Si and BCC alloy were doped to the NaBH4-MgH2 system. Among these catalysts, TiF3 exhibited the optimum behavior in terms of fast kinetics and lowering the dehydrogenation temperature of the NaBH4-MgH2 system. The rehydrogenation experiments of TiF3-doped NaBH4-MgH2 system were investigated at 600℃ with an initial hydrogen pressure of about 4MPa. It showed that 5.89 wt.% hydrogenwas rehydrogenated within 12 h. XRD results demonstrated the formation of NaBH4 and MgH2 in the rehydrogenated sample.