Hydrogen sorption properties were investigated for selected mixtures of MgH2 and carbon materials, including graphite, activated carbon, multi-walled carbon nanotubes (MWCNTs), carbon nanofibres (CNFs) and activated carbon fibres. The introduction of such carbon materials decreases the decomposition temperature of MgH2. The best results were achieved in the mixtures involving CNFs and MWCNTs, with metallic impurities, particularly nickel and iron, inherited from the original synthesis. The peak temperatures of MgH2 decomposition were reduced to 322 and 341°C, respectively, compared with 360°C for simply milled MgH2. Substantial improvement in the decomposition kinetics of MgH2 was achieved, particularly with CNF additions. The MgH2 decomposition was completed within 20min at 300°C with a 5wt.% CNF addition, compared to 240min for simply milled MgH2. The improved kinetics was maintained even after several hydriding–dehydriding cycles. X-ray diffraction and transmission electron microscopy reveal that some structural changes occur after cycling: there is an increase in particle size of the MgH2 phase, with separation between the magnesium and carbon phases, indicating a clear relationship between the decomposition temperature of MgH2 and its structure. It has also been shown that the presence of carbon materials prevents MgH2 particle growth which, in turn, enhances its decomposition.