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Abstract The interaction between active materials and conductive additives is complicated but crucial within electrochemical energy storage devices. Here, we first identify that CH 2 groups drive the compositing process, leading to an effective formation of Co-O-C chemical bonding serving as the bridge between reduced graphene oxide(rGO) and hydroxide. Due to the enhanced electron transport, a dramatically improved specific capacity is achieved as high as 1368 F/g for rGO/Co(OH) 2 electrode at a current density of 0.5 A/g. Thus, we provide new insights into graphene/hydroxide compositing mechanism, which has a significant impact on enhancing electron transport for a variety of graphene/hydroxide in energy storage systems. Highlights • CH 2 groups transform into Co-O-C bonds as the bridge between graphene and Co(OH) 2. • rGO/Co(OH) 2 exhibits a highly crystalline feature. • BG/Co(OH) 2 holds more Co3+ ions and Co-O tetrahedral structures. • C-(O-Co) n affords abundant electron transport channels. • A dramatically high specific capacity of 1368 F/g is achieved for rGO/Co(OH) 2. Graphical abstract Image 1 [ABSTRACT FROM AUTHOR]