The nanoparticles generally show abnormal properties compared to those in the bulk phase, and they exhibit significant potential in various applications such as catalysis and energy conversion. However, the theoretical work for describing the properties of nanoparticles is limited with poor prediction capacity. In this work, the Gibbs free energy was studied, from both macroscope and microscope, predictive models were proposed to study the thermodynamic properties of nanoparticles with a generalized description of the Gibbs free energy considering the effects of surface‐energy and the substrate contacted. The proposed model from the microscope was based on the corresponding states theory to describe the effect of the substrate on the Gibbs free energy of nanoparticles, in which the molecular parameter with a generalized constant was obtained from the melting point of metals due to sufficient experimental information. The comparison with the new measured experimental results proves the reliability of the model prediction. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4595–4603, 2017