The invention discloses an anti-corrosion organic silicon adhesive for inner wall of desulfurization chimney and a preparation method thereof. The preparation method comprises following steps: preparing a component A, mixing 107 silicone rubber, fumed silica, silicon powder, silicone oil, kaolin, and a deep curing addictive together to prepare the component A; preparing a component B, mixing a cross-linking agent, tackifier, catalyst, silicone oil, fumed silica and carbon black to prepare the component B, and mixing the component A and the component B according to a certain ratio to prepare an anti-corrosion organic silicon adhesive for inner wall of desulfurization chimney. The anti-corrosion organic silicon adhesive for inner wall of desulfurization chimney has the advantages of high tensile strength, excellent elongation at break, high shear strength, long operation time, convenience for on-site construction, fast deep curing, and good adhesivity and elasticity, and is capable of applying to the fields of anti-corrosion of inner wall of desulfuration chimney and adhesive bonding and coating of various light glass bricks.