Nicola Sturgeon and Rishi Sunak will speak over the telephone on Tuesday evening before Mr Sunak concludes his first day in office as Prime Minister.
A Scottish government spokesperson confirmed a conversation would take place between the pair.
Earlier this month, Ms Sturgeon told the BBC’s political editor Chris Mason she had not had a conversation with former prime minister Liz Truss since she was appointed on September 6, other than “an exchange or two” at events following the death of the Queen.
“It’s quite absurd in many ways. When I became First Minister, David Cameron was prime minister and I think we spoke on the phone the first night I became First Minister,” she said.
“I spoke on the phone to Theresa May within a day or two of her becoming prime minister, same with Boris Johnson actually.
“I have deep political differences with all of these politicians, but we have a duty to work together constructively.”
During the summer leadership election, Ms Truss came under fire for saying she would “ignore” Ms Sturgeon.
She said previously: “I think the best thing to do with Nicola Sturgeon is ignore her.
“She’s an attention seeker, that’s what she is.
Meanwhile, the SNP branded Mr Sunak’s ongoing cabinet reshuffle as “dangerous” after he re-appointed Suella Braverman as Home Secretary.
The party’s Westminster deputy leader Kirsten Oswald, said: “Rishi Sunak’s Cabinet of Truss re-treads makes the case once again that independence is the only route to escape Westminster chaos for good.
“From a Justice Secretary who doesn’t believe in the Human Rights Act or economic and social rights to a fired then rehired Home Secretary with a twisted dream of deporting vulnerable people.
“A dangerous Cabinet imposed upon Scotland by the new unelected, out of touch, law-breaking Prime Minister.
“It’s beyond any doubt that only with the full powers of independence will we be able to escape the Tory chaos, Tory-made economic crisis, and build a fairer, more prosperous society.”
Scottish Labour leader Anas Sarwar also hit out at Ms Braverman’s reappointment.
He tweeted: “So much for “leading with integrity and compassion”.
“Braverman sacked for a security breach … dreams of planes to Rwanda … back at the heart of government.
“Different face, different suit – same divisive and chaotic ideology.”
Alex Cole-Hamilton, Scottish Lib Dem leader, called Alister Jack “the great survivor” after his reappointment and accused him of “keeping his head down” during the political crisis engulfing the government over the last few months.
“Alister Jack is proving to be the great survivor but has only done so by keeping his head down and staying silent when people needed to take a stand,” he said.
“Rewarding Boris Johnson’s loyalists with Cabinet positions shows that this is still the same old Conservative party.
“The scandal-prone, out of touch and economically ruinous Conservative party is not fit to govern. That’s why we need an immediate general election.
“Scottish Liberal Democrats are ready to play our part in removing this government.”
