Dethroned last year by the Chinese city, Luanda regained the dubious honour despite the depreciation of the local kwanza currency against the dollar, according to the survey by the Mercer consulting group.
While Hong Kong is bounced back down to second place it remains the most expensive Asian city "because of its currency's link to the dollar, a factor which makes local housing more expensive," the report said.
After topping the Cost of Living report for three consecutive years, Luanda was pipped by the Asian city in 2016, owing to a stronger Hong Kong dollar.
The survey compares the cost of over 200 items in over 200 cities, including housing, food, transport and entertainment.
It takes New York (in ninth place this year) as its base for comparison and measures currency movements against the dollar.
The study is closely followed by governments and international businesses which take the rankings into account when they calculate the costs of sending their employees abroad.
Some Russian cities leapt up the table in the new survey, with Moscow reaching 14th place from 53rd last year and Saint Petersburg leaping to 36 from 116 "under the twin effects of the rise in the ruble and the cost of goods and services".
Lots of European cities were on the way down, particularly in Britain due to the weakness of the pound. Paris, Vienna and Rome also became less expensive for the expat purse.
At the bottom of the table were the Macedonian capital Skopje, Kyrgyzstan capital Bishkek and Tunisia's capital Tunis.
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