Duplex formation between DNA-based monomers creates linear, polymeric assemblies that resemble larger duplex DNA, but in which the main chain is defined by the reversible base pairing. These monomers provide a reversible polymer platform through which molecule-to-material relationships can be explored. Viscometry, static and dynamic light scattering, and size exclusion chromatography are used to probe the size, structure, and dynamics of the systems. The influence of concentration, temperature, association constant, and conformational. flexibility is examined and found to be consistent with simple equilibrium models. The characterizations provide the basis for further mechanistic studies of reversible polymeric behavior in complex environments.