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Electrospun WO3 nanofibers were fabricated by coaxial electrospinning and directly annealing WCl6/polyvinylpyrrolidone (PVP) nanofibers on activated carbon fibres (ACF), and characterized by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The most suitable condition for electrospinning is the mass ratio of WCl6 to PVP 0.6, appropriate amount DMF and ethanol, a voltage of 28 kV, the reception distance of 15 cm, the humidity range within 10% and 20% and the moving rate of the pump 0.001 mm/s. The photocatalytic activities of WO3 nanofibers were evaluated by the photo-degradation of phenol solution under the irradiation of 500 W xenon lamp. The results showed that, the sizes of the fibers are about 100 nm, and after being photodegraded for 210 min, the concentration of phenol decreased from 20.05 mg/L to 8.60 mg/L. Thus, the photo-degradation rate of WO3 nanofibers for phenol solution is 2.87 mg/(L·h).