In this paper the bulk, surface and interfacial structures of a series of polyureas containing polydimethylsiloxane segments are examined. The silicone polyureas studied here all contain 25wt% of a 5,000 molecular weight aminopropyl-terminated polydimethylsiloxane diamine, along with various ratios of a 900 molecular weight polypropylene oxide diamine soft segment and hard segments comprised of isophorone diisocyanate and 1,3 diamino pentane chain extender. The bulk morphology and rheology of the silicone polyureas are studied using transmission electron microscopy, differential scanning calorimetry, and dynamic mechanical thermal analysis. The siloxane segments are observed to form well-phase-separated spherical microdomains, while the matrix phase is comprised of a mixture of the polypropylene oxide soft segments and the hard segments. The single glass transition temperature of the matrix phase increases systematically as the ratio of hard segment to polypropylene oxide soft segment increases. The surfaces of the silicone polyureas are characterized using contact angle analysis, X-ray photoelectron spectroscopy and static secondary ion mass spectrometry. All of the silicone polyureas exhibit a thin 15 to 20 Angstrom overlayer of the siloxane segments at their surface. The ability of the silicone polyurea surfaces to restructure upon contact with either water or an acid-functional acrylate pressure sensitive adhesive is also studied. The extent and rate of decrease in the receding water contact angle, as a function of water dwell time and temperature. are related to the segmental mobility within the near-surface region of the silicone polyurea coatings. Silicone polyureas having higher hard segment content, and higher non-silicone matrix glass transition temperatures, are better able to maintain a high water receding contact angle, due to their lower segmental mobility. The observed increases in adhesion of the pressure sensitive adhesive, with increasing aging time and/or temperature, are attributed to an increase in the acid-base interactions between urea groups in the silicons polyurea and acrylic acid groups in the PSA. The initially low peel forces can be more readily maintained for the silicone polyureas having high hard segment contents, due to the reduced segmental mobility and reduced degree of interfacial restructuring within the silicone polyurea.