TiO2/PS, Fe(III) tetraphenylporphyrin (FeTPP)/PS and TiO2/FeTPP/PS nanofibers were prepared by electrospinning a mixture solution of corresponding compounds in N,N-dimethylformamide (DMF). The absorbance of FeTPP was characterized by UV-vis spectroscopy. The surface morphologies of these electrospun mats were evaluated with scanning electron microscope (SEM). Their photocatalytic activities were examined with the photodegradation reaction of methyl orange in aqueous solution under the irradiation of visible light. The result shows that the photocatalytic activity of TiO2/FeTPP/PS mat is higher than that of FeTPP/PS mats, which in turn is better than that of TiO2/PS mats in the photodegradation of methyl orange. The degradation percent of methyl orange could be up to 97.8% in 3 h by the FeTPP/TiO2/PS mat photocatalyst.