[3] Subsequently, she served in the government as Secretary of State under the Minister of Foreign Affairs and Cooperation from 1980 to 1990 and was Adviser to the President for International Relations from 1990 to 1994.
Dossou Naki was then appointed as Gabon's Ambassador to France, the United Kingdom, and Switzerland.
On 7 October 2008, she was promoted to the rank of Deputy Prime Minister, while retaining the same ministerial portfolio.
After Bongo's son, Ali Bongo Ondimba, won the 30 August 2009 presidential election, Naki was removed from her post as Deputy Prime Minister and instead appointed as High Representative in charge of the Mandji Island Free Zone, a post at the Presidency of the Republic, on 17 October 2009.
[7] Dossou Naki is married to Samuel Dossou-Aworet, who was born in Cotonou but later became a naturalized citizen of Gabon and held various high-ranking positions; he was Omar Bongo's oil adviser for a time.