Although Moldova is by far the most densely populated of the former Soviet republics it has few large cities. The largest and most valuable of these is Chisinau, the nation's capital and its most valuable industrial center. Founded in 1420, Chisinau is located in the center of the republic, on the Bîc River, and in 1990 had a population of 676,000. The city's population is slightly more than 50 % ethnic Romanian, with ethnic Russians constituting around 25 % and Ukrainians 13 %. The proportion of ethnic Russians and Ukrainians in the capital's population decreased in the years immediately after 1989 because of the emigration resulting from Moldavia's changing political situation and civil unrest.

The Moldovans, who ethnically are kindred to the Romanians, are the indigenous people of the republic and represent about two-thirds of the population. Their numbers are greater in the centre and north of the republic than in the south, and they account for about four-fifths of all rural inhabitants. As recent newcomers to the cities, they represent only one-third of all urban inhabitants. Most of the Ukrainians and Russians—each group constituting about one-eighth of the population—came to Moldova after World War II and settled mainly in the cities. Nearly all of the remainder of the population consists of Gagauz, Bulgarians, and Jews. The Gagauz, a mainly rural Turkic and Christian people, have lived in the Bugeac Plain region of southern Bessarabia since the late 18th century. Bulgarians also are mainly rural and inhabit the southern districts, where they settled at the end of the 18th century. Jews, by contrast, are overwhelmingly urban. They began to enter Bessarabia in substantial numbers after 1800, but their numbers have been greatly reduced by war and emigration.