This article present results on the preparation, characterization, and application of fibrous polymer mat-supported Fe(III) mesotetraphenylporphyrin (FeTPP)/TiO2 photocatalysts for the photodegradation of azo-dyes. Scanning electron microscope results showed that the mean diameters of FeTPP/TiO2/polymer mats were in the range of 246.0-305.6 nm. Photocatalytic activities of these hybrid nanofibers were evaluated by the photocatalytic degradation of methyl orange in an aqueous environment under the visible light irradiation. Results showed that chlorinated polyvinyl chloride and poly(styrene) (PS) fibrous mats were the two best supporting materials for the FeTPP/TiO2 photocatalyst. PS fibrous mats supported the fact that the FeTPP/TiO2 photocatalyst (FeTPP/TiO2/PS mat) could degrade methyl orange up to 98.5% in 5 h. Furthermore, the FeTPP/TiO2/PS mat also exhibited high and stable photocatalytic activity toward four other azo-dyes. The FeTPP/TiO2/PS mat might find application in the preparation of a membrane photo-reactor for continuous wastewater treatment.