Studies of protein binding domains reveal molecular architectures with specific chemical moieties that provide a framework for selective recognition of target biomolecules in aqueous environment. By matching functionality and positioning of chemical residues, we have been successful in designing biomimetic polymer networks that specifically bind biomolecules in aqueous environments. Our work addresses the preparation, behavior, and dynamics of the three-dimensional structure of biomimetic polymers for selective recognition via non-covalent complexation. In particular, the synthesis and characterization of recognitive gels for the macromolecular recognition of D-glucose is highlighted. Novel copolymer networks containing poly(ethylene glycol) (PEG) and functional monomers such as acrylic acid, methacrylic acid, and acrylamide were synthesized in dimethyl sulfoxide (polar, aprotic solvent) via UV-free radical polymerization. Polymers were characterized by single and competitive equilibrium and kinetic binding studies, single and competitive fluorescent and confocal microscopy studies, dynamic network swelling studies, DPC, and FE-SEM. Results qualitatively and quantitatively demonstrate effective glucose-binding polymers in aqueous solvent. Due to the presence of template, the template mediated polymerization process resulted in a more macroporous structure as exhibited by dynamic swelling experiments, confocal microscopy, and SEM. Recognitive networks had a more macroporous structure with absorption of water occurring via non-fickian diffusion at a faster rate and with a higher equilibrium value. Polymerization kinetic studies suggest that the template molecule has more than a dilution effect on the polymerization, and the effect of the template is related strongly to the rate of propagation. The processes and analytical techniques presented are applicable to other biologically significant molecules and recognitive networks, in which hydrogen bonding, hydrophobic, or ionic contributions will direct recognition. Further developments are expected to have direct impact on applications such as analyte controlled and modulated drug and protein delivery, drug and biological elimination, drug targeting, tissue engineering, and micro- or nano-devices.