A three-dimensional (3D) free-standing network composed of cross-linked carbon@ Au core-shell nanofibers was fabricated by combining the electrospinning technique and an in situ reduction approach. The results showed that a uniform Au layer of approximately 5 nm thickness was formed around the electrospun carbon nanofiber. What's more, it's interesting to note that the Au layer was composed of small Au nanoparticles. And, the as-prepared CNFs@Au network exhibited excellent catalytic activity for the reduction of 4-nitrophenol (4-NP) based on the electron-rich catalytic platform arising from the synergistic effect between carbon and Au. Notably, the free-standing 3D nanofibrous cross-linked network structure could improve the catalyst's performance in separation and reuse.