Three rhenium-doped nickel catalyst surfaces including Re-Ni(111), Re-Ni(200) and Re-Ni(220) were built via Re atom substituting one atom of upper layer Ni surfaces. The sulfurated poisoning process involving H2S adsorption and subsequent splitting steps (H2S→HS+H, HS→S+H) on the three surfaces was investigated and further compared using density functional theory (DFT) to understand the crystal-plane effect. For H2S adsorption, the H2S molecule is preferentially adsorbed on the Re top and bridge ReNi1 sites. Re-Ni(200) surface possessed lower H2S adsorption energy compared to Re-Ni(111) and Re-Ni(220) surfaces, due to its smaller coordination number and higher d-orbital intensity at Fermi level. For splitting steps, transition state search showed that the two processes on the three surfaces are all calculated as exothermic while the energy barrier is basically in the range of 0.23 eV∼0.44 eV, which signifies that the poisoning process is favorable both kinetically and thermodynamically. The splitting steps can be described as a dynamic procedure that contains intimate HS fragment activation, S–H bond stretching accompanied by H atom departure and final dissociation into HS+H or S+H co-intermediates. The valence bond changes during dissociation deduced from projected density of states (PDOS) analysis also proved the above procedure.