The adhesive properties of certain types of biopolymer can be used to increase the residence time of orally or nasally administered drugs. A fuller understanding of the molecular processes underpinning such ‘mucoadhesive’ phenomena will help in the optimal design of delivery systems. The interactions involved are, however, less well defined compared with those often encountered in protein-recognition phenomena: mucoadhesive interaction products can be very large and polydisperse, so to probe them we need to adopt a different strategy to those used by protein biochemists. Reviewed herein is some of the recent work at physiological or near-physiological solution conditions involving molecular hydrodynamics – with analytical ultracentrifugation and SEC-MALLs (size-exclusion chromatography coupled to multi-angle laser light scattering) as the cornerstones – reinforced by viscometry and the imaging probes of electron microscopy and atomic force microscopy. These clearly demonstrate the mucoadhesive properties of both an unusual cationic protein [Deacon, Davis, Waite and Harding (1998) Biochemistry 37, 14108–14112] and more significantly chitosan polysaccharides of varying degrees of charge/acetylation as a function of solution conditions, and are providing the platform for the construction of stable formulations.