The association of the 4 aminoazobenzene (4AA) by two different water-soluble hosts, β-Cyclodextrins (β-CD) and calixarenesulfonates (CnS), was studied in heterogeneous conditions using molecular simulations. This situation is achieved by immobilization of macrocycles onto a gold Au (111) surface. Severals factors that can influence the binding properties are investigated here through the chain length of alkylthiols spacer of the surface-immobilized host and the number of attachments points to the surface. A conformational change of β-CD as a function of the chain length is evidenced upon grafting on the gold surface whereas CnS does not show any changes. It is then possible to tune the thermodynamic properties of β-CD by changing the grafted chain length and forming a larger hydrophobic region. The mechanisms of insertion of the guests into the cavities are similar to those obtained in homogeneous system. Whereas the 4AA is included longitudinally in the β-CD cavity, it interacts rather with the sulfonate groups at the outer edge of the cavity.