Based on density functional theory, we investigated the hydrogen evolution reaction (HER) of AgTe. We implemented the Vienna Ab initio Simulation Package to compute the model systems. The exchange-correlation energies were described by Perdew–Burke–Ernzerhof functional with generalized gradient approximation. We optimized the structure until the forces were less than 10^-3 eV/Å, and the energy tolerance was set to 10^-6 eV. To understand the reaction performance of AgTe, we computed the electronic structures and the Gibbs free energy difference (ΔG_H) of hydrogen adsorption on a 2-nm-thick AgTe (001) slab. Our computational results show that the AgTe slab is metallic, while bulk has a small bandgap of 0.35 eV. Six different binding sites for a hydrogen atom were evaluated for the slab structure, and ΔG_H varied from -0.005 eV to 0.33 eV. Considering that HER is more advantageous when the value of ΔG_H is close to zero, the values prove that AgTe surfaces provides active sites to the reaction. We concluded that differences in ΔG_H originate from the atomic geometries at the surface, which affect orbital hybridization.