Carbon nanofibers composite catalyst (Cu/CNFs) were developed by homogeneous polymeric solution based electrospinning and high temperature carbonization process in situ. The newly developed catalyst was thoroughly characterized through a series of characterization methods. The catalyst was carried out Ullmann coupling of N-heterocyclic compounds, N-arylationreaction and a wide range of aryl halides, and the catalyst performed excellent catalytic activity, selectivity and recyclability.