Ellipsometry configurations in internal reflection mode facilitate studies of adsorption processes without the light beam passing through the medium from which adsorption accurs. Monitoring of adsorption processes on surfaces in opaque media is thus possible. If the surface in addition has a thin semitransparent metal film in which surface plasmon polaritons can be excited, one can achieve very high sensitivity to small changes in surface mass density of an adsorbed biolayer. Thickness changes as small as on pm can be resolved. In this chapter the theory for Total Internal Reflection Ellipsometry (TIRE), also called surface plasmon resonance enhanced ellipsometry, will be described and instrumentation will be briefly discussed. TIRE applied in spectroscopic as well as in angle of incidence interrogation modes will be considered. Finally applications in the areas of bioadsorption processes, biosensing, gas adsorption and biolayer imaging will be reviewed.