In order to improve the hydrogen storage performance of MgH2, graphene and CeF3 co-catalyzed MgH2 (hereafter denoted as MgH2+CeF3@Gn) were prepared by wet method ball milling and hydriding, which is a simple and time-saving method. The effect of CeF3@Gn on the hydrogen storage behavior of MgH2 was investigated. The experimental results showed that co-addition of CeF3@Gn greatly decreased the hydrogen desorption/absorption temperature of MgH2, and remarkably improved the dehydriding/hydriding kinetics of MgH2. The onset hydrogen desorption temperature of Mg + CeF3@Gn is 232 °C,which is 86 °C lower than that of as-milled undoped MgH2, and its hydrogen desorption capacity reaches 6.77 wt%, which is 99% of its theoretical capacity (6.84 wt%). At 300 °C and 200 °C the maximum hydrogen desorption rates are 79.5 and 118 times faster than that of the as-milled undoped MgH2. Even at low temperature of 150 °C, the dedydrided sample (Mg + CeF3@Gn) also showed excellent hydrogen absorption kinetics, it can absorb 5.71 wt% hydrogen within 50 s, and its maximum hydrogen absorption rate reached 15.0 wt% H2/min, which is 1765 times faster than that of the undoped Mg. Moreover, no eminent degradation of hydrogen storage capacity occurred after 15 hydrogen desorption/absorption cycles. Mg + CeF3@Gn showed excellent hydrogen de/absorption kinetics because of the MgF2 and CeH2-3 that are formed in situ, and the synergic catalytic effect of these by-products and unique structure of Gn.