The Ukraine Kiev Mission currently covers the central and southern portions of the country. The first missionaries arrived in October 1990, when the area (and much of eastern Europe) belonged to the Austria Vienna East Mission. In February 1992, the Ukraine Kiev Mission was formed. During 1992, missionaries went outside of Kiev for the first time, going to Donetsk, Gorlovka, and Khar'kov. In July 1993, the Ukraine Donetsk Mission was formed.
For the first several years, all missionary work was conducted in Russian, which is the primary language of many Ukrainians in the eastern part of the country. With the availability of the Book of Mormon in Ukrainian, the first missionaries were called to speak Ukrainian in 1996. This allowed the work to expand quickly into the western part of the country which predominantly speaks Ukrainian. Since the late 1990s, the mission has been a predominantly Ukrainian speaking mission, with some missionaries still called to speak Russian.
In 1998, the church announced their intention to construct a temple in Kiev. The temple was dedicated August 29, 2010.
In 2011, the Ukraine Dnipropetrovsk mission was formed, mainly from cities originally in the Donestak mission. The Lviv mission was announced in 2013 and will include western Ukranian cities originally in the Kiev mission.
Additional relevant historical details are included in this article about the history of the Donetsk mission, including a map of the 4 missions in Ukraine.