Nanomaterials have excellent adsorption performance, which mainly depends on the adsorption thermodynamics that is related to the shape of the nanoparticles that make up the nanomaterial, but the effects of shape on the thermodynamics of adsorption are not fully clear. In this paper, theoretically, the general formulae of adsorption thermodynamic properties for nanoparticles with different shapes and different sizes were derived, and the influencing regularities and mechanisms on adsorption thermodynamic properties were discussed. Experimentally, the influences of the shape and size of nano-CeO2 on the thermodynamics of adsorption were studied in aqueous solution. The experiment results showed that the shape has significant influences on the thermodynamics of adsorption, and the smaller the particle size, the more significant the effects of shape on the thermodynamics. For the adsorption of nano-CeO2 with different shapes and the same equivalent particle size, compared with the sphere, the equilibrium constant of adsorption for the octahedron is larger, while the molar Gibbs free energy of adsorption , the molar adsorption enthalpy of adsorption and the molar adsorption entropy of adsorption are smaller. For the adsorption of nano-CeO2 with the same shape, with the decreasing particle size, increases, while , and decrease; and , , and are each linearly related to the reciprocal of particle size. The experimental results are consistent with the theoretical relations. The theories can quantitatively describe the adsorption behavior on nanoparticles, explain the regularities and mechanisms of influence of shape, and provide guidance for the research and application of nanoadsorption.