The invention relates to the field of photocatalytic materials, and in particular relates to a preparation method of a high-specific-surface porous TiO2 nano-fiber. According to the preparation method, the nano-fiber is obtained by dissolving out SiO2-phase nano-particles in a double-phase SiO2-TiO2 electrostatically-spun nano-fiber by adopting a solvent dissolution method, wherein the solvent is one of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, cesium hydroxide or hydrofluoric acid. The preparation method disclosed by the invention regulates the dissolution rate of SiO2 in the double-phase SiO2-TiO2 nano-fiber by means of regulating the pH value, temperature, concentration and dissolution time of the solvent so as to regulate the appearance of a microstructure of the nano-fiber. The double-phase SiO2-TiO2 nano-fiber is prepared by mixing organism precursors of titanium and silicon, adding high polymer, performing electrostatic spinning, and then roasting by adopting a roasting method. The preparation method disclosed by the invention is simple in process and low in preparation cost, the target product has high photocatalytic activity and porosity, and the pore size distribution is centralized.