Lipid-based liquid crystalline compositions of phospholipids and diglycerides have unique bioadhesive properties with several medical applications, as exemplified by a lipid-based medical device indicated for management and relief of intraoral pain. The present paper describes the relation between self-assembly properties of phosphatidyl choline (PC) and glycerol dioleate (GDO) mixtures in the presence of aqueous fluids and functional attributes of the system, including: film formation and bioadhesion, intraoral coverage, acceptance by patients, and potential as a drug delivery system. The phase behavior of PC/GDO was characterized using synchrotron small-angle X-ray scattering. Functional properties, including the presence of study formulations at intraoral surfaces, ease of attachment, taste, and degree of and intraoral pain, were assessed in a crossover clinical pilot study in head and neck cancer patients. An optimum in functional properties was indicated for formulations with a PC/GDO weight ratio of about 35/65, where the lipids form a reversed cubic liquid crystalline micellar phase structure (Fd3m space group) over the relevant temperature range (25-40 degrees C).