Based on density functional theory, a first-principles study of the adsorption behavior of hydrogen atoms on the PuO2(111) surface is carried out in this work. Models for three different surface morphologies of PuO2(111) are established. It is found that the surface with the outermost oxygen atom (sub outer Pu atom) morphology has the best stability. Based on this model, the adsorption energy, bader charge, and electronic density of the states of a hydrogen atom at different adsorption sites are calculated. Finally, we analyzed the process of hydrogen dissociation into hydrogen atoms on the surface using the cNEB method. The results indicate that the top position of the outermost oxygen atom and the bridge position of the second outermost plutonium atom are relatively stable adsorption configurations, where hydrogen atoms lose electrons and release heat, forming O-H bonds with oxygen atoms. The density of states of O-p orbital electrons will undergo significant changes, reflecting the hybridization of O-p and H-s orbital electrons, forming a stable bonding effect. The dissociation of hydrogen molecules into two hydrogen atoms adsorbed on the top of oxygen atoms requires crossing an energy barrier of 1.06 eV. The decrease in total energy indicates that hydrogen tends to exist on the PuO2(111) surface in a hydrogen atom state. The research results lay the foundation for theoretically exploring the hydrogenation corrosion mechanism of the PuO2(111) surface, providing theoretical support for exploring the corrosion aging of plutonium oxide, predicting the material properties of plutonium oxide under extreme and special environments.