The band inversion in topological phase matters bring exotic physical properties such as the topologically protected surface states (TSS). They strongly influence the surface electronic structures of the materials and could serve as a good platform to gain insight into the surface reactions. Here we synthesized high-quality bulk single crystals of Co3Sn2S2 that naturally hosts the band structure of a topological semimetal. This guarantees the existence of robust TSS from the Co atoms. Co3Sn2S2 crystals expose their Kagome lattice that constructed by Co atoms and have high electrical conductivity. They serves as catalytic centers for oxygen evolution process (OER), making bonding and electron transfer more efficient due to the partially filled orbital. The bulk single crystal exhibits outstanding OER catalytic performance, although the surface area is much smaller than that of Co-based nanostructured catalysts. Our findings emphasize the importance of tailoring TSS for the rational design of high-activity electrocatalysts.