Abstract We report observations of the Didymos–Dimorphos binary asteroid system using the Atacama Large Millimeter/submillimeter Array (ALMA) and the Atacama Compact Array (ACA) in support of the Double Asteroid Redirection Test mission. Our observations on UT 2022 September 15 provided a preimpact baseline and the first measure of Didymos–Dimorphos’s spectral emissivity at λ = 0.87 mm, which was consistent with the handful of siliceous and carbonaceous asteroids measured at millimeter wavelengths. Our postimpact observations were conducted using four consecutive executions each of ALMA and the ACA spanning from T+3.52 to T+8.60 hr, sampling thermal emission from the asteroids and the impact ejecta. We scaled our preimpact baseline measurement and subtracted it from the postimpact observations to isolate the flux density of millimeter-sized grains in the ejecta. Ejecta dust masses were calculated for a range of materials that may be representative of Dimorphos’s S-type asteroid material. The average ejecta mass over our observations is consistent with 1.3–6.4 × 10 7 kg, with the lower and higher values calculated for amorphous and crystalline silicates, respectively. Owing to the likely crystalline nature of S-type asteroid material, the higher value is favored. These ejecta masses represent 0.3%–1.5% of Dimorphos’s total mass and are in agreement with lower limits on the ejecta mass based on measurements at optical wavelengths. Our results provide the most sensitive measure of millimeter-sized material in the ejecta and demonstrate the power of ALMA for providing supporting observations to spaceflight missions.