Solvent deasphalting is a highly efficient process for removing asphaltene and metals from the petroleum residue; however, there are rare modeling studies about the interaction between metals and asphaltene. This work establishes the association models of metals (Ni and V) with asphaltene during solvent deasphalting. The models reveal that the distribution factors of metals are related to the solvent density, association enthalpy, and temperature. The association energy of metalasphaltene is higher than that of metal-resin. The distribution factor of metals with asphaltene is lower than that without asphaltene. The tuned model could well-predict the distribution factors for both Ni and V. The models provide the thermodynamics and theoretical guide for removing the metals from the heavy oil during solvent deasphalting.