Hydrogen spillover is a crucial process in the selective hydrogenation reactions on Pd/Cu single atom alloy catalysts. In this study, we report the atomic-scale perspective of these processes on the single atom alloy catalyst Pd/Cu(111) based on the experimental and theoretical results, including infrared reflection absorption spectroscopy (IRAS), temperature programmed desorption (TPD), high-resolution X-ray photoelectron spectroscopy (HR-XPS), and density functional theory (DFT) calculations for core-level excitation. The hydrogen spillover onto Cu(111) was successfully observed in real time using time-resolved IRAS measurements at 80 K. The chemical shifts of Pd 3d5/2 indicate that H2 is dissociated and adsorbed at the Pd site. In addition, a "two-step" chemical shift of the Pd 3d5/2 binding energy was observed, indicating two types of hydrogen adsorption states at the Pd site. The proposed mechanism of the hydrogen dissociation and spillover processes is as follows: (i) a hydrogen molecule is dissociated at a Pd site, and the hydrogen atoms are adsorbed on the Pd site; (ii) the number of hydrogen atoms on the Pd site increases up to three; and (iii) the hydrogen atoms will spill over onto the Cu surface.