Polymer- and small-molecule-based organic electronic devices are being developed for applications including electroluminescent displays, transistors, and solar cells due to the promise of low-cost manufacturing. It has become clear that these materials exhibit nanoscale heterogeneities in their optical and electrical properties that affect device performance, and that this nanoscale structure varies as a function of film processing and device-fabrication conditions. Thus, there is a need for high-resolution measurements that directly correlate both electronic and optical properties with local film structure in organic semiconductor films. In this article, we highlight the use of electrical scanning probe microscopy techniques, such as conductive atomic force microscopy (c-AFM), electrostatic force microscopy (EFM), scanning Kelvin probe microscopy (SKPM), and similar variants to elucidate charge injection/extraction, transport, trapping, and generation/recombination in organic devices. We discuss the use of these tools to probe device structures ranging from light-emitting diodes (LEDs) and thin-film transistors (TFT), to light-emitting electrochemical cells (LECs) and organic photovoltaics.