The area of the district was split off from Mueang Ubon Ratchathani district and formed a minor district (king amphoe) on 1 April 1991.[1] It was upgraded to a full district on 5 December 1996.[2]
The name Don Mot Daeng meaning "upland of red ant".
The district is divided into four sub-districts (tambons), which are further subdivided into 46 villages (mubans). There are no municipal (thesaban) areas, and four tambon administrative organizations (TAO).