Hydrogen storage properties of LaN4.25Al0.75 alloy were experimentally investigated by XRD, PC isotherm curves, hydrogen absorption kinetics curves, XPS and its particle diameter. The structure of unit cell of LaNi4.25Al0.75 alloy was deduced. The relationship between its structure and hydrogen storage performance of LaNi4.25Al0.75 alloy was analyzed. The results show that LaNi4.25Al0.75 alloy has rapid hydrogen absorption rate and good resistance to combustibility. It is also found that the function of the hydrogen absorption plateau pressure and temperature is ln peq=-4 820/T+12.46, and the hydrogen absorption rate of the alloy decreases with increasing the temperature.