The cyclodextrin dimer (trans-Azo ?-CD Dimer) and the adamantyl modified polyacrylamide (PAM-Ad) were synthesized. A supramolecular system was constructed by the formation of inclusion complex between trans-Azo ?-CD Dimer and PAM-Ad. The results of 2D NMR measurement indicated that the host-guest interaction between trans-Azo ?-CD Dimer and PAM-Ad was carried out through the formation of inclusion complexes between ?-CD cavity and the hydrophobe Ad. The interaction between trans-Azo ?-CD Dimer and PAM-Ad was depended on the concentration of trans-Azo ?-CD Dimer,PAM-Ad and the photoisomerization of trans-Azo ?-CD Dimer. The influences of salt concentration and temperature on the viscosity of mixture solution were also studied.