Poly(dimethylsiloxane) (PDMS) networks were fluorescently labeled with the 1-(dimethylamino)-5-naphthalenesulfonyl (dansyl) chromophore. The networks were prepared by end-linking silanol-terminated PDMS with a mixture of methyltriethoxysilane (MTES) and N-((triethoxysilyl)propyl)dansylamide (DTES). The selective sorption behavior of these networks swollen in binary mixtures of 1,4-dioxane and a series of water and linear alcohols was studied. Refractometry and equilibrium swelling measurements were used to determine the amounts of PDMS and solvent components inside the swollen networks. We find that the cosolvency behavior of the solvent mixture depends on the alkyl chain length of the amphiprotic solvent. Steady-state fluorescence spectra of the dansyl compound dissolved in binary solvent mixtures are compared to the fluorescence of dansyl-labeled networks swollen with the same solvent mixture. Differences in emission energy are related to differences in the polarity of the solvation shells surrounding the dansyl moieties. The composition around the labeled cross-link junctions is compared with the bulk composition to determine spatial heterogeneity in the distribution of solvent and polymer molecules. We find that while dioxane is preferentially sorbed, the alcohols preferentially solvate the fluorescent moieties. Water has a tendency to cluster inside the networks that is stronger than its tendency to preferentially solvate dansyl.