For wastewater contaminated with organic dyes commonly found in textile industry, titanium dioxide (TiO2) has been used as a catalyst to speed up the degradation of these dyes so the wastewater will be treated before releasing to nature or being recycled. Various forms of TiO2 have been studied in this process. In this study, a novel form of TiO2 was proposed and successfully fabricated. The fabrication of TiO2/Polymer fibrous composite was successfully prepared via electrospinning technique. By wrapping the fibrous composite around a spherical metal-wire structure, the novel form of this composite was prepared. Various parameters such as polymer concentration, type of solvent, applied voltage and percentage of added TiO2 had been studied. The optimum electrospinning condition was chosen so that the desired form of fiber was prepared. The obtained catalyst ball was then characterized its ability to be used as a catalyst in the photo-degradation of methylene blue used as an organic dye model in this study. The UV-visible spectrometry was employed to determine the degree of degradation of studied organic dye. The results showed that this novel form of TiO2 catalyst still had TiO2’s characteristics as a catalyst and can be used in the wastewater treatment of organic dye contaminated water. However, the metal structure added more advantages including helping stabilized the immersion of TiO2 in wastewater and also making the recovery much more effective to the system. Moreover, another form of TiO2/Polymer fibrous composite with magnetic particles embedded was also reported for the comparison.