Porous carbon nanostructures with hetero-atom doping are regarded as a promising anode candidate for rechargeable alkalis ion batteries. Herein, a novel boron-doped 3D hierarchical porous carbon network (B-CN) was prepared via a unique in situ double-template (NaCl and HBO3) method. The as-obtained B-CN with high specific surface area (480 m(2) g(-1)), high-defect B-doping (2.74 at. %) and high volume of hierarchical pores (1.28 cm(3)/g) exhibits a reversible capacity as high as 200 mAh g(-1) at 0.1 A g(-1) after 100 cycles and superior rate capability of 189 mAh g(-1) at 5 A g(-1) for Na-ion batteries. It also exhibits excellent cycling performance (496 mAh g(-1) after 100 cycles at 0.1 A g(-1)) and rate capacity (285 mAh g(-1) at 5 A g(-1)) in Li-ion batteries. The outstanding electrochemical performance of B-CN can be attributed to the large surface area with more active sites produce by B-doping, short ions diffusion length and continuous electrons transport pathway provided by 3D hierarchical porous carbon architecture. Moreover, the surface-dominated redox reaction rendered by our tailored B-doped carbon nanostructures is a promising strategy for developing electrode materials with high rate capability. The convenient synthesis process offers a new tactic in fabricating high performance energy storage device.