The objective of this work is to study the effects of altering the chain building blocks and the reaction on template binding and transport parameters of imprinted polymer gels. The characterization of imprinted poly(diethylaminoethylmethacrylate-co-hydroxyethylmethacrylate-co-polyethyleneglycol(n)dimethacrylate) polymer gels prepared via free (FRP) or living (LRP) radical polymerization with varying crosslinking monomer lengths (number of ethylene glycol repeat units of 1, approximate to 4.5, approximate to 9) and concentrations (1, 5, 10, 50%) is presented. All imprinted networks prepared via LRP exhibited significantly higher template binding affinities and capacities as well as significantly lower template diffusion coefficients compared to those prepared via FRP. Synthesizing imprinted polymers via LRP results in much smaller and relatively constant dispersities of polymer chains compared to imprinted polymers prepared via FRP. Therefore, LRP has a profound structural effect on the imprinted polymer network leading to increased homogeneity in the mesh structure which enhances the molecular imprinting effect. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3588-3599, 2013