Organic optoelectronic materials are used in a variety of devices, including light-emitting diodes, field-effect transistors, photovoltaics, thermoelectrics, spintronics, and chemico- and biosensors. The processes that determine the intrinsic optoelectronic properties occur either in the photoexcited states or within the electron-pumped charged species, and computations that predict these optical and electrical properties would help researchers design new materials. In this Account, we describe recent advances in related density functional theory (DFT) methods and present case studies that examine the efficiency of light emission, carrier mobility, and thermoelectric figures of merit by calculation of the electron–vibration couplings.