This work highlights the rational design of recognitive networks via polymerization reaction analysis and detailed kinetic analysis for application in novel diagnostic or robust point-of-care devices. Non-covalent complexation interactions between template or 'guest' biomolecules and functional monomers during polymerization can create networks with selective binding sites for biomolecules within polymeric films. The concept of macromolecular recognition manifests itself from two major synergistic effects, (i) shape specific molecular cavities that match the template biomolecule and (ii) structured chemical groups oriented to form multiple complexation points with the template molecule. The resulting polymer networks are selective due to the particular chemistry of the binding site, the orientation and stabilization of the chemistry in a crosslinked matrix, as well as by the size and shape of the site for the template biomolecule. Polymerization reactions of acrylate and methacrylate based templated systems were analyzed to increase the ability to tailor the functional design of networks with specific interest in template affinity, selectivity, loading, and diffusional properties. This work highlights that the final polymer composition does not represent feed compositions when using significant amounts of short bi-functional crosslinking monomer (i.e., intramolecular distances between crosslinking monomer double bonds are short). Additionally, this work highlights the use of living polymerization techniques for the formation of recognitive polymeric structures. Living free radical polymerization has shown to dramatically increase the loading capacity of recognitive systems while retaining selectivity for a specific biomolecule.