The construction of polymer networks through host-guest complexation between the beta-cyclodextrin (beta CD) substituents of 6(A)-(1-(2-aminoethyl)amino)-6(A)-deoxy-beta-cyclodextrin 2, 3, and 6% randomly substituted poly(acrylate) (PAA beta CDen) and the adamantyl (AD) substituents of 1-(2-aminoethyl)amidoadamantyl 2, 3, and 6% randomly substituted poly(acrylate) (PAAADen) is reported. A 2D H-1 NOESY NMR spectroscopic study shows the formation of host-guest complexes by the beta CD and AD substituents. This is characterized by a complexation constant, K-1 = 3020 +/- 60 mol(-1) dm(3), for 3% substituted PAA beta CDen and PAAADen as shown by isothermal titration calorimetry. The viscosity of a 2 wt % equimolar mixture of 3% randomly substituted PAA beta CDen and PAAADen reaches a maximum at [NaCl] = 0.1 mol dm(-3), and the viscosity and the storage and loss moduli (G' and G '') increase with the increase in degree of substitution from 2 to 6%.