Water diffusion in polymer composites is not only affected by the chemical nature of the materials but also by their internal structures. To enable the design of polymer composites with controlled diffusion kinetics, we investigate the effect of hydrogel particle networks on the water transport. The composites in this study comprise hydrogel particles based on sodium poly(acrylic acid), which are incorporated at different concentrations into a soft and sticky polymer matrix. Through the use of X-ray micro computed tomography, the internal structure of the polymer composites is examined and the interparticle distances are calculated. The structure of the composites is then related to the water diffusion kinetics upon exposure to saline solution as well as humid air. Even though the hydrogel particles are isolated and the interparticle distances are in the order of several micrometers, a sudden increase in the water diffusion kinetics is observed above a critical concentration. Due to the low water permeability of the matrix, such a change in the water diffusion kinetics is indicative of network formation. During hydration, swelling enables the hydrogels to overcome the interparticle distances and form a network for water transport.