An emission sensor/sampler system was coupled to a National Aeronautics and Space Administration (NASA) hexacopter unmanned aerial vehicle (UAV) to characterize gases and particles in the plumes emitted from open burning of military ordnance. The UAV/sampler was tested at two field sites with test and sampling flights spanning over 16 h of flight time. The battery-operated UAV was remotely maneuvered into the plumes at distances from the pilot of over 600 m and at altitudes of up to 122 m above ground level. While the flight duration could be affected by sampler payload (3.2–4.6 kg) and meteorological conditions, the 57 sampling flights, ranging from 4 to 12 min, were typically terminated when the plume concentrations of CO2 were diluted to near ambient levels. Two sensor/sampler systems, termed “Kolibri,” were variously configured to measure particulate matter, metals, chloride, perchlorate, volatile organic compounds, chlorinated dioxins/furans, and nitrogen-based organics for determination of emission factors. Gas sensors were selected based on their applicable concentration range, light weight, freedom from interferents, and response/recovery times. Samplers were designed, constructed, and operated based on U.S. Environmental Protection Agency (EPA) methods and quality control criteria. Results show agreement with published emission factors and good reproducibility (e.g., 26% relative standard deviation for PM2.5). The UAV/Kolibri represents a significant advance in multipollutant emission characterization capabilities for open area sources, safely and effectively making measurements heretofore deemed too hazardous for personnel or beyond the reach of land-based samplers.