A close correllation between molecular-level interactions and macroscopic characteristics of polymer networks exists. The characteristics of the polymeric hydrogels assembled from beta-cyclodextrin (beta-CD) and adamantyl (AD) substituted poly(acrylate)s can be tailored through selective host-guest complexation between beta-CD and AD substituents and their tethers. Dominantly, steric effects and competitive intra- and intermolecular and host-guest complexation are found to control poly(acrylate) isomeric inter-strand linkage in polymer network formation. This understanding of the factors involved in polymeric hydrogel formation points the way towards the construction of increasingly sophisticated biocompatible materials.