The invention provides a preparation method of a novel ionic binuclear Schiff base titanium complex and a synthetic method of applying the novel ionic binuclear Schiff base titanium complex to catalyze zinc powder and reduce disulfide or selenide to prepare sulfo(seleno) ester and dissymmetric sulfoether(selenide). The complex is a cationic binuclear Schiff base titanium complex, wherein titaniumatoms are bridged by oxygen atoms and are coordinated with a Schiff base ligand and a hydrone, and an ionic bond is formed by a cation part and an anion part of whole Schiff base titanium. The ionic binuclear Schiff base titanium complex is used as a catalyst, the zinc powder is used as a reducer, the disulfide(selenide) can be reduced and fractured, and the disulfide(selenide) can further and respectively react with anhydride, an alpha-bromo carbonyl compound and bromoalkane to prepare the sulfo(seleno) ester and the dissymmetric sulfoether(selenide). According to the preparation method provided by the invention, the defects that traditional lewis acid halide is deliquescent, an absolute solvent is used, conditions are strict and the like are overcome; an effective path for reducing the disulfide or selenide to prepare the sulfo(seleno) ester and the dissymmetric sulfoether(selenide) is provided, and the preparation method has the advantages of high yield, simpleness in operation andthe like.