A Fe modified Na2WO4 compound was synthesized by a solution impregnation method and was ball-milled with MgH2 to constitute a novel MgH2-Fe2O3/Na2WO4 composite. The effects of the Fe2O3/Na2WO4 additive on the hydrogen storage properties of MgH2 together with the corresponding mechanism were investigated. At 423 K, within the first 200 seconds, the hydrogen absorption amount of MgH2+20 wt％ Fe2O3/Na2WO4 was almost 5 times that of pure MgH2. And at 573 K, its total hydrogen desorption amount was 7 times that for pure MgH2. Meanwhile, its onset dehydrogenation temperature was 110 K lower than that of pure MgH2. It was worth noting that the MgH2+20 wt％ Fe/Na2WO4 presented the lower dehydrogenation reaction activation energy (Ea) of 35.9 kJ·mol-1 compared to that of pure MgH2. The active MgWO4, Mg2FeH6 and MgO formed during the milling process were responsible for the improvement of the hydrogen storage properties for MgH2.