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The current study highlights important information regarding how graphene oxide (GO) additive interacts with magnesium hydride (MgH₂) and transforms to reduced graphene oxide (rGO). A mild reduction occurs during mechanical milling itself, whereas a strong reduction of GO happens concurrently with the oxidation of Mg formed during the dehydrogenation of MgH₂. Owing to the in situ transformation of GO to rGO, the dehydrogenation temperature of MgH₂ reduces by about 60 °C, whereas the hydrogen ab/desorption reaction kinetics of MgH₂ increases by two orders of magnitude and the dehydrogenation activation energy decreases by about 20 kJ/mol. We have thoroughly scrutinized the transformation of GO to rGO by differential scanning calorimetry (DSC), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM) techniques. Interestingly, the GO to rGO transformation triggered by magnesium hydride in the current study further paves the way for the facile preparation of rGO- and MgO-decked rGO composites, which are important materials for energy storage applications.