Nuclear magnetic resonance (NMR) relaxation and q-space diffusion measurements have been used to probe the microscopic water distribution in a variety of starch-based systems, including packed beds of native starch granules with varying water contents, starch gels, and freeze-dried starch gels. The q space data for the granular beds is compared with a variety of theoretical models and conforms best to unbounded diffusion in a lower dimensional space. In contrast to some earlier reports, the data for the gelatinized samples are not anomalous and conform to simple unrestricted diffusion in a three-dimensional space, The paper concludes with a novel method for probing pore size distribution in freeze-dried starch gels by infusion of acetone. (C) 1998 Elsevier Science Inc.