The release process of three osmotically active solutes with various solubilities in water (NaCl, CsNO3, and CsCl) from silicone rubber matrices is presented. The kinetics of release for different initial loads of the salts were supplemented by measurements of the kinetics of concurrent water uptake. To gain insight on the relevant non-Fickian transport mechanisms, the morphology, the diffusion and sorption properties and the physicochemical state of water in the salt-depleted matrices were studied. In addition, both salt-loaded and salt-depleted matrices were characterized with respect to their mechanical properties. The combined information, derived from these techniques, supported the operation of a release mechanism carried out through the formation of microscopic cracks, interconnecting the permanently formed cavities inside the matrices. The results indicate that these microscopic cracks may have healed upon drying. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 113: 936-949, 2009