Hydrogen purification and storage are critical issues in the transportation application of hydrogen fuel. Herein, we report that hydrogen can be separated from other components during its storage in Li3N, when the steam-reforming product of natural gas is employed as the hydrogen source. The kinetics and capacity of hydrogen absorption of Li3N are not affected by CO2, and only the kinetics is slightly affected by CO. During desorption, the hydrogen stored in Li3N can be released, thus providing a pure hydrogen source for fuel cells or other applications. The simultaneous separation of hydrogen during its storage tremendously reduces the cost of the hydrogen fuel for transportation and also provides a novel process for hydrogen purification.