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Effective reduction and inhibition of restacking are critical steps in realizing the full potential of chemically derived graphene. In this manuscript, we report a one-step, all solid-state microwave procedure for simultaneous reduction and concurrent growth of carbon nanotubes 'spacers' on graphene from a single precursor, namely hydroquinone. Our newly developed technique not only effectively reduces graphene oxide but also results in vertically anchored carbon nanotubes on graphene substrate to give unique mesoporous, hierarchical carbon nano-architectures. When applied as a negative electrode in lithium-ion batteries, our 3D graphene-carbon nanotube hybrids exhibit a high capacity of 1016 mA h g À1 with a columbic efficiency of 98% even after prolonged cycling.