Modulation of the structural parameters of multivinyl hydrogels allows optimization of their permeability, which is a prerequisite for different biomedical applications. However, only a few studies to date have been reported regarding macromolecular diffusion within divinyl and multivinyl systems, and even less provide information about the correlation of diffusion to the network characteristics. Therefore, this study aimed to understand the permeability performance of tailored poly(vinyl alcohol) (PVA) multivinyl hydrogels and correlating it to the network characteristics using two common theories: rubber elasticity and equilibrium swelling. A systematic increase in the number of functional groups per PVA backbone successfully modulated the PVA physicomechanical properties. These modifications resulted in varying the hydrogel permeability performance to solutes of different sizes and shapes. Correlating the network characteristics to macromolecular permeability of hydrogels proved the reliability of applying the equilibrium swelling theory for hydrogel mesh size estimation over the rubber elasticity theory. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014, 52, 63-72