Starting in 1994, Klyuyev was a deputy chairman of the
Donetsk Oblast Executive Council. From November 1995 to April 1996 he was a Deputy Head of the Donetsk Oblast State Administration, responsible for local development, trade, and consumer goods production. After a career in Donetsk Oblast, and at the time working closely with later and current
President Viktor Yanukovych, Klyuyev moved to national politics. On 14 December 2001, Klyuyev was elected the deputy chairman of the
Party of Regions. At the
2002 election, he became a member of the
Verkhovna Rada for the
Party of Regions, working as head of the Energy, Nuclear Policy and Nuclear Safety Committee. On 19 April 2003, at the 5th Party Congress Klyuyev was elected the secretary of the party's political council. From 2003 to 2004, Klyuyev was the Energy
Vice Prime Minister in the
First Yanukovych Government. NSDC secretary sees Azarov as likely candidate for premiership. On 24 January 2014, President Yanukovych signed a decrees that dismissed Klyuyev as National Security and Defense Council secretary and appointed him head of the
Presidential Administration of Ukraine. Klyuyev resigned from this post. Since 7 March 2014 he is wanted for involvement in
mass murder. The day before the
EU froze his assets. In June 2019, the
Central Election Commission of Ukraine refused Klyuyev to register for 21 July
2019 Ukrainian parliamentary election as a candidate for the
Liberal Party of Ukraine in Electoral District 46 situated in
Donetsk Oblast because he had not lived in Ukraine for 5 years. The same day the Central Election Commission registered Klyuyev's candidacy. In 2025, the Ukrainian government imposed sanctions against Klyuyev. ==International sanctions==