In this work, a uniform heterojunction of cupric oxide/cuprous oxide was decorated on the surface of carbon fibers by electrochemical method (CuO/Cu2O/CDs/CFs). Methyl-beta-cyclodextrin was first grafted on the surface of carbon fibers (CDs/CFs). Cubic cuprous oxide was electrodeposited on the surface of (Cu2O/CDs/CFs) in 0.1 M KNO3, the cuprous oxide was then partly anodized to cupric oxide to form a heterojunction of cupric oxide/cuprous oxide with a burr shape (CuO/Cu2O/CDs/CFs). The obtained materials were characterized by field emission scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electrochemical techniques. The potential application in pollution treatment was further investigated, and the prepared CuO/Cu2O/CDs/CFs could be a promising adsorbent/photocatalyst toward the uptake and degradation of 2, 6-dichlorophenol (2, 6-DCP).