Ni(0) porous carbon nanofibers (Ni(0)/PCNFs) were successfully synthesized by a simple electrospinning technique with subsequent process of reduction and calcination. The as-prepared continuous Ni(0)/PCNFs which had a uniform particles diameter of 5 nm and porous structure were adopted as a catalyst in Heck reaction, which effectively improved the conversion and the selectivity of the product. Compared with Ni(0) supported on carbon nanofibers, the solid nanoporous catalyst obviously increases the efficiency of Heck reaction and also does not require ligands. Though five recycles, the catalyst remained a high catalytic activity.