Larijani was the Secretary of the Supreme National Security Council from 15 August 2005 to 20 October 2007, appointed to the position by President Mahmoud Ahmadinejad,[10] replacing Hassan Rouhani.

[11] Larijani was one of the two representatives of the Supreme Leader of the Islamic Revolution Ali Khamenei to the council, the other being Hassan Rouhani.

[12] In his post as secretary, he effectively functioned as the top negotiator on issues of national security, including Iran's nuclear program.

[13] Initially, he wanted to continue his graduate studies in computer science, but changed his subject after consultation with Morteza Motahhari.

[16] In March 1994, he was appointed as head of the Islamic Republic of Iran Broadcasting, replacing Mohammad Hashemi Rafsanjani in the post.

[23] However, on 22 October 2012, during a QA meeting with the students of Iran University of Science and Technology, Larijani denied the allegations that he had congratulated Mousavi.

Considering Larijani's long career as an Islamic Republic insider who has been part of the top echelons of power since the 1979 revolution, his disqualification was a possibility even his staunch detractors couldn't envision.

[27] Iranian scholar Mehdi Moslem in his 2002 book named Factional Politics in Post-Khomeini Iran, suggests that Larijani had been a member of Motalefeh and part of the ‘traditional right’.

[28] Payam Mohseni, a fellow at the Belfer Center for Science and International Affairs, classifies Larijani as a lead figure in the ‘theocratic right’ camp, whose other prominent are Mahmoud Hashemi Shahroudi and Mohammad Reza Mahdavi Kani.

[31] During Iranian 2016 parliamentary election Larijani was the leader of the Followers of Wilayat faction,[32] although he was backed by the reformist List of Hope and said he is running as an independent candidate.

[34] According to a poll conducted in March 2016 by Information and Public Opinion Solutions LLC (iPOS) among Iranian citizens, Larijani has 45% approval and 34% disapproval ratings and thus a +11% net popularity, while 11% of voters do not recognize the name.

[13] Larijani is the son-in-law of Ayatollah Morteza Motahhari,[13][39] His daughter, Fatemeh Ardeshir-Larijani, studies at the University Hospitals Cleveland Medical Center in the United States.