The noble metal such as Pt has been used as the catalysts for hydrogen evolution reaction (HER), but with problems such as scarcity of resources and high cost. Anchoring transition metal atoms onto the catalysts is regarded as a potential approach to solve this problem and enhance the electrocatalytic performance of HER. For this purpose, two-dimensional materials, such as CuPS3 monolayer, are regarded as one of the most ideal carriers for adsorption of metal atoms. However, there is no previous study on this topic. In this paper, we systematically studied microstructures, electronic properties and electrocatalytic performance of the CuPS3 monolayer anchored with transition-metal atoms (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) using a density functional theory (DFT). Results showed that all the transition metal atoms are favorably adsorbed onto the CuPS3 monolayer with large binding energies at the top of the Cu atom. The pristine CuPS3 monolayer has a large catalytic inertia for hydrogen evolution reactions, whereas after anchored with transition metal atoms, their catalytic performances have been significantly improved. The Gibbs free energy (ΔGH) is 0.44 eV for the H atom absorbed onto the pristine CuPS3 monolayer, whereas the ΔGH values for the V, Fe, and Ni atoms anchored onto the CuPS3 monolayer are 0.02, 0.11, and 0.09 eV, respectively, which is close to the ΔGH of H atom adsorbed on Pt (e.g., -0.09 eV). At the same time, the influence of hydrogen coverage rate was calculated. The result shows that V adsorbed on CuPS3 monolayer is catalytic active for HER for a large range of hydrogen coverage. Our results demonstrate that anchoring of V atom onto the CuPS3 monolayer is a potentially superior method for making the catalyst for the HER.