"Some bully governments -- I really don't know of any more appropriate term for some foreign figures and leaders than the word bullying -- insist on negotiations," Khamenei told officials after Trump threatened military action if Iran refuses to engage in talks on its nuclear programme.
"Their negotiations are not aimed at solving problems, they aim at domination," Khamenei said.
On Friday, Trump said he had written to Iran's supreme leader, urging new talks on the country's nuclear programme but warning of possible military action if it refuses.
Foreign Minister Abbas Araghchi said Iran had yet to receive any letter from the US president by Saturday.
"We have heard of it (the letter) but we haven't received anything," he told state television.
Khamenei accused the bullying powers of deliberately setting new conditions they did not expect Iran to meet.
"They are setting new expectations that they think will definitely not be met by Iran," he said, without naming the United States or referring to Trump's comments.
On Friday, Araghchi told AFP in an interview that Iran would not negotiate under "maximum pressure".
The policy, reinstated by Trump on his return to the White House in January, saw him reimpose sweeping sanctions on Tehran during his first term after abandoning the nuclear accord formally known as the Joint Comprehensive Plan of Action (JCPOA).
Struck between Tehran and major powers in 2015, the deal had offered relief from sanctions in exchange for limits on Iran's nuclear activities.
Tehran has in recent months engaged in diplomatic efforts with the three European parties to the deal -- Britain, France and Germany -- aimed at resolving issues surrounding its nuclear ambitions.
However on Saturday, Khamenei condemned the three governments for "declaring that Iran has not fulfilled its nuclear commitments under the JCPOA".
"You say that Iran has not fulfilled its commitments under the JCPOA. Okay, have you fulfilled your commitments under the JCPOA?" he asked.
- Peaceful nature -
Khamenei recalled that Tehran had abided by the terms of the JCPOA for a whole year after Trump abandoned it in 2018 before beginning to roll back on its own commitments.
He said there had been "no other way" following legislation by the Iranian parliament.
Iran has since sharply ramped up its enrichment of uranium far beyond the limits set by the JCPOA.
US officials now estimate that Iran could produce a nuclear weapon within weeks if it chose to do so.
Tehran has consistently denied pursuing a nuclear arsenal, emphasising the peaceful nature of its programme.
Officials have always cited a religious decree issued by Khamenei that prohibits the development of such weapons.
Last month, Khamenei reiterated his opposition to negotiations with the United States, calling the idea "unwise" after Trump called for a new nuclear deal.
Khamenei charged that Washington "ruined, violated, and tore up" the 2015 agreement.
In 2019, more than a year after Trump's withdrawal from the JCPOA, Japan's then prime minister Shinzo Abe visited Iran in an attempt to mediate.
But Khamenei firmly rejected the possibility of talks with Washington, saying he did not "consider Trump as a person worthy of exchanging messages with".
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