Abstract Water-based anti-corrosion coatings, which are environmentally-friendly replacements for organic solvent-based coatings, do not perform well enough for use in the most challenging corrosion environments. The high water absorption capacity of water-based latex films may reduce barrier performance by contributing to corrosive reactant/product transport. We seek to understand the coupled effects of water absorption and ion transport in hydrated latex films, and to propose mechanisms explaining these effects. Water absorption and ion transport in films immersed in deionized (DI) water were monitored by mass gain and electrical conductivity measurements, respectively. Despite very similar polymer compositions between films, large differences in water absorption and ion transport rates were observed and explained by percolating networks at latex particle boundaries which facilitate transport. A semi-continuum model with three-component diffusion and convection-like elastic relaxation supported the assumptions of the physical mechanisms governing water absorption and ion transport. The evidence of the coupled processes of water absorption and ion transport in hydrated latex films revealed in this study are useful for designing water-based coatings that provide high levels of corrosion resistance.