Interest has emerged in the development of devices based on organic materials and low energy, low cost, roll-to-roll fabrication techniques. Two specific target applications have received particular attention: organic transistors to enable macroelectronics (large area displays, RFID tags, etc.) and organic photovoltaics. Common to both applications is the development of optimal inks: for macroelectronics, small crystallizable molecules in an inert polymer binder, for photovoltaics, fullerene based acceptors blended in an active polymer donor. Critical to a proper understanding of the device performance is an understanding of the vertical profile of the fabricated film. For thin film transistors, segregation of the small molecule semiconductor to the interfaces is essential. For PV, segregation of the fullerene can be both advantageous (if at the cathode) and deleterious (if at the anode). Spectroscopic ellipsometry studies of the vertical profile are daunting, as the systems are in general anisotropic with individual component spectra that are strongly dependent on the local order. We present SE studies of both TFTs and OPV devices using a multiple sample approach to remove correlations in the resultant models. The optical depth profiles are compared to both NEXAFS studies of the interface composition and neutron reflectivity studies of similar processed films. We find good agreement between the SE and less model dependent techniques. The studies illuminate general principles of the influence of interfacial free energy on the resultant segregation of the species.