Organic light-emitting devices (OLEDs) are attractive for use in next-generation display and lighting technologies. In display applications, OLEDs offer a wide emission color gamut, compatibility with flexible substrates, and high power efficiencies. In lighting applications, OLEDs offer attractive features such as broadband emission, high-performance, and potential compatibility with low-cost manufacturing methods. Despite recent demonstrations of near unity internal quantum efficiencies (photons out per electron in), OLED adoption lags conventional technologies, particularly in large-area displays and general lighting applications. This thesis seeks to understand the optical and electronic properties of OLED materials and device architectures which lead to not only high peak efficiency, but also reduced device complexity, high efficiency under high excitation, and optimal white-light emission. This is accomplished through the careful manipulation of organic thin film compositions fabricated via vacuum thermal evaporation, and the introduction of a novel device architecture, the graded-emissive layer (G-EML). This device architecture offers a unique platform to study the electronic properties of varying compositions of organic semiconductors and the resulting device performance. This thesis also introduces an experimental technique to measure the spatial overlap of electrons and holes within an OLED's emissive layer. This overlap is an important parameter which is affected by the choice of materials and device design, and greatly impacts the operation of the OLED at high excitation densities. Using the G-EML device architecture, OLEDs with improved efficiency characteristics are demonstrated, achieving simultaneously high brightness and high efficiency.