TiO2, as a kind of traditional photocatalytic material, has been widely used in wastewater treatments due to its cost-efficiency, high stability and low toxicity. However, it could hardly be reused and might lead to secondary pollution. In the study, porous electrospun polycaprolactone (PCL) fibrous mats were used as carriers for the capacity and dispersion of TiO2. The porous PCL mats could provide large contact area for high photocatalytic efficiency of TiO2. Besides, the addition of rectorite (REC) could reduce the diameters of fibers and enlarge the specific surface area, which might be beneficial to photocatalysis. More importantly, REC played an important role in improving the function of porous PCL/TiO2 mats, which contributed to a high rate of photocatalytic degradation. The results indicated that porous PCL/TiO2/REC mats could serve as potentially excellent photocatalysts in the degradation of organic dyes.