First-principle study based on density functional theory are used to scrutinize the mechanism of H₂S adsorption and dissociation over Rh(110) surface. For adsorption mechanisms, we probe the most favorite sites of H₂S monomers over Rh(110) surface. It is determined that H₂S vigorously adsorbed over high symmetry adsorption sites with preferred long-bridge (LB) site having adsorption energy − 1.00 eV, with no more than 0.50 eV, binding energy. Also we found that HS chemisorption is higher as compared to H₂S on Rh(110) surface having − 3.76 eV adsorption energy, where atomic S and H binding at hollow and short-bridge site is more stronger. The energy barriers to split the bond of S–H in first and second H₂S dehydrogenation are 0.18–0.36 and 0.30 eV. To further investigate, electronic density of state are employed to illustrate the interaction of adsorbed H₂S with the surface of Rh(110), which is able to account for energy divergences of all species adsorbed on Rh(110) surface. Hence, our calculated results confirm that H₂S dissociation over Rh(110) surface is exothermic as well as an easy process, however kinetically and thermodynamically the existence of atomic S avoid the breaking of H–S bond procedure.