Considering the efficient TiO2 structure on enhancing its photocatalytic behavior is of great interest in recent years. Meanwhile, inhibiting the filtration process for detachment of the catalyst from the purified solution is very advantages. To approach this purpose, TiO2 nanofiber yarns were successfully fabricated through the electrospinning technique using two oppositely charged nozzles followed by the calcinations process from a solution containing titanium precursor and polyvinyl acetate (PVAc) as the supporting material. The introduced nanofiber yarns eliminate the ultrasonic and centrifuge steps required in photocatalytic tests of nanoparticles and electrospun nanofibers. The results show that this new catalyst's structure maintains its shape during the photocatalytic degradation process and can be easily removed from the purified water.