Fabrication of hierarchical nanostructures is an important way for performance improvement and application expansion of nanomaterials. It is still a great challenge to synthesize three dimensional hierarchical graphene nanostructures with controlled secondary structures and primary building units, because it is difficult to realize effective control of graphene layer morphology and necessary arrangement of graphene. In this work, a "complex-directed" strategy has been successfully developed for the synthesis of three dimensional graphene nanostructures. Especially, the obtained three dimensional graphene nanostructures are quite regular in morphology, they can be nanorods or regular particles, composed of hollow graphene nanospheres with different layers. The morphology and the structure of these nanostructures, including primary building units and secondary structures are strongly dependent on the amount of HCl solution. The obtained three-dimensional graphene nanostructure can serve as an excellent candidate for electrode material of electric double layer capacitors (EDLCs) and present outstanding electrochemical behaviors. This is mainly due to the excellent electrical conductivity of graphene hollow nanospheres and the porous structures conducive to ion diffusion and electron transport. (C) 2020 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.