The development of metalated covalent organic frameworks (COFs) is useful for generating recyclable catalytic systems for practical applications. Herein, we report the synthesis, characterization, and catalytic properties of an azine-linked twodimensional (2D) COF containing nickel-doped dehydrobenzoannulene (DBA) units. We demonstrate that Ni-DBA-2D-COF can be used to reductively cleave the aryl C−S bonds of several organosulfur compounds utilizing dimethylethylsilane as the reducing agent. The Ni-DBA-2D-COF catalytic system displays excellent recyclability and good yields. This work highlights a rare example of utilizing metalated DBA complexes to perform catalytic transformations.