We report on the first systematic ground-based validation of the US Air Force Defense Meteorological Satellite Program’s Operational Linescan System (DMSP-OLS) night lights imagery to detect rural electrification in the developing world. Drawing upon a unique survey of villages in Senegal and Mali, this study compares night-time light output from the DMSP-OLS against ground-based survey data on electricity use in 232 electrified villages and additional administrative data on 899 unelectrified villages. The analysis reveals that electrified villages are consistently brighter than unelectrified villages across annual composites, monthly composites, and a time series of nightly imagery. Electrified villages appear brighter because of the presence of streetlights, and brighter villages tend to have more streetlights. By contrast, the correlation of light output with household electricity use and access is low. We further demonstrate that a detection algorithm using data on night-time light output and the geographic location of settlements can accurately classify electrified villages. This research highlights the potential to use night lights imagery for the planning and monitoring of ongoing efforts to connect the 1.4 billion people who lack electricity around the world.