The sulfate ions immobilization behavior of calcined layered double hydroxides (CLDHs) in the hardened cement paste was investigated. The experimental results show that the sulfate ions in cement paste are immobilized by CLDHs to reconstruct the layered structure and aggregate around CLDHs. The immobilization amount of sulfate ions by CLDHs reaches 4.74×10-3 mol/g, while the increasing amount indicates non-linear relation with the addition of CLDHs. The incorporation of CLDHs decreases the amount of ettringite formed to limit the expansion of cement paste, which decays the sulfate reaction to enhance the sulfate resistance of concrete.