Carbon nanotube/graphene-based one-dimensional nanostructure was successfully synthesized via electrospinning and heat treatments. During the electrospinning process, nanofibers with evenly distributed graphene and PS nanobeads were synthesized. During the post-heat-treatment process, the pores were generated by decomposition of PS. Finally, CNT-RGO-CoSe₂-C-composite was synthesized through subsequent oxidation and selenization. CNT-RGO-CoSe₂- C-composite showed high discharge capacity of 390 mA h g^-1 after 500 cycles at 1.0 A g^-1. The high sodium-ion storage properties were attributed to the synergetic effect of CNT/graphene-based materials with high electrical conductivity.