A novel photocatalyst, nano-sized zinc and cobalt phthalocyanines (MPc), are anchored on polyacrylonitrile (PAN) nanofibers in the presence or absence of TiO2 and the process was realized with an innovative solution blow spinning (SBS) method for the first time. Novel nanofiber composites were characterized by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy techniques. According to the SEM micrographs, the immobilization of nano-Pcs on the surface of PAN nanofibers was uniform and does not involve agglomeration. The MPc/PAN composite yielded nearly complete degradation of methylene blue (MB) of a highly photocatalytic nature. It was also found that the presence of TiO2 on MPc/PAN composite have no effect on photodegradation of MB. Also, the recycling of new photocatalysts required as little change as possible owing to their macroscopic structure and their flexible nature.