PFG NMR results are reported on H2O, PEG200, PEG1500, PEG8000, and PEG20000 in wet cotton fibers and H2O in wet cotton linters. The data are analyzed in terms of a two-site exchange model (water/cotton) and show that the probe molecules in fibers are trapped in cages. The cage size decreases froth 10 to 2 mum as the probes' size increases from 0.23 to 9.2 nm, although the overall accessible volume only decreases from 50 to 20-30%. This behavior may be explained by size-exclusion effects on the connectivity and accessibility. Analysis of the diffusion coefficients at short diffusion times indicates that fiber cages are water pools held between the growth rings of the fiber. In linters these cages do not occur, and a freely diffusing signal from H2O in the amorphous region is observed with D = (4.5-8.9) x 10(-11) m(2) s(-1), which when compared to the predicted value from the microviscosity of the amorphous regions gives a tortuosity of 2-4. Exit of all probes from linters and fibers takes 0.2 s and requires hydrogen bonds to be broken with an activation energy of 50 kJ mol(-1).