Abstract The present paper deals with the synthesis and hydrogenation behaviour of graphitic nanofibres. The GNF were grown by thermal cracking of hydrocarbon gases (ethylene, acetylene) at a temperature of 600°C for a time duration of 2 h. The structural characterizations have been evaluated by X-ray diffraction and transmission as well as scanning electron microscopy. It was found that the as grown graphitic nanofibres, unlike graphite, have preferred orientations corresponding to (101). The hydrogenation behaviour was studied through charging at a pressure of 120 atm. and then discharging at a pressure up to 1 atm. The P–C–T curve drawn based on several dehydrogenation runs has revealed the GNF to have hydrogen storage capacity of ∼10 wt%.