Photocatalysts are the most important technology in air pollution removal and the detoxification of organic materials. Doping and complexation are among the most used methods to improve the efficiency of photocatalysts. Titanium dioxide and zinc oxide nanomaterials are widely used materials for photocatalysts and the degradation of toxic materials. Their mixed structure can be fabricated by many methods and the structure affects their properties. Nanofibers are efficient materials for photocatalysts due to their vertically formed structure, which improves the charge separation of photoelectrons. We fabricated them by an electrospinning process. A precursor consisting of titanium 4-isopropoxide, zinc acetate dihydrate and polyvinylpyrrolidone was used as a spinning solution for a mixed structure of titanium dioxide and zinc oxide with different molar ratios. They were then calcined, crystallized by heat treatment and analyzed by thermogravimetric-differential thermal analysis (TG-DTA), X-ray diffractometer (XRD), field emission scanning electron microscope (FE-SEM) and energy-dispersive spectroscope (EDS). After annealing, the average diameters of the Ti–Zn complex oxide nanofibers were 237.6–278.6 nm with different salt ratios, and multiple crystalline structures were observed, namely TiO2, ZnO, ZnTiO3 and Zn2TiO4. We observed the photocatalytic performance of the samples and compared them according to the photodegradation of methylene blue. The methylene blue concentration decreased to 0.008–0.650 after three hours, compared to an initial concentration of 1, with different metal oxide structures.