This work demonstrated the enhanced photodegradation (PD) resulting from Co-rich doping of ZnO nanowire (NW) surfaces (Co2+/ZnO NWs) prepared by combining Co sputtering on ZnO NWs and immersion in deionized water to exploit the hydrophilic–hydrophobic transitions on the ZnO surfaces resulting from Co atom diffusion. Because of the controllable spin-dependent density of states (DOS) induced by Co2+, the PD of methylene blue dye can be enhanced by approximately 90% (when compared with bare ZnO NWs) by using a conventional permanent magnet with a relatively low magnetic field strength of approximately 0.15 T. The reliability of spin polarization–modulation attained through surface doping, based on the magnetic response observed from X-ray absorption measurements and magnetic circular dichroism, provides an opportunity to create highly efficient catalysts by engineering surfaces and tailoring their spin-dependent DOS.