The abundance of organic pollutants in environment has persuaded researchers to establish an advanced technology and address this global issue. We discovered that graphene incorporated p-type CuO/n-type TZB-Gr (Copper Oxide/Titanium dioxide-Zinc Oxide-Bismuth Oxide-Graphene) heterojunctions nanofibers (NFs) with band gap of (1.7eV) can effectively produce active radicals to degrade most of the organic pollutant to become CO2 and H2O. One-dimensional electrospun (NFs) of p-type CuO/n-type TZB-Gr heterojunctions with high visible and UV-light activity were successfully synthesized using sol-gel and a facile electrospinning technique. The results show that the CuO/TZB-Gr (NFs) were 75 nm in diameter and multi-micrometers in length. The as prepared electrospun (NFs) were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), UV-vis diffuse reflectance (DR) spectroscopy, resonant Raman spectroscopy and thermogravimetric analysis (TGA). Kinetic study of composite CuO/TZB-Gr (NFs) was carried out. Compared with commercial P25 particles, the as prepared p-type CuO/n-type TZB-Gr (NFs) disclosed a strikingly higher photocatalytic activity in the degradation of Methylene Blue (MB) and formaldehyde. The enhanced photocatalytic activity of MB under Visible and UV light and formaldehyde under Visible light could be regarded to the formed p-n heterojunction between CuO and TZB-Gr and their higher separation efficiency of photogenerated electrons and holes. Moreover, due to one-dimensional nature of p-type CuO/n-type TZB-Gr heterojunctions, these (NFs) could be easily reused without the decrease of photocatalytic efficiency, therefore rendering a novel strategy for environmental applications.