During the Ankara talks, Larijani and Solana will be looking to see if there is scope for a new round of negotiations to end the crisis over Iran’s atomic programme, which the West fears could be diverted to make nuclear weapons.
"I expect to have a resumption of the talks that we had some time ago and see if we can move toward negotiations," Solana said as he confirmed the talks ahead of a meeting of EU foreign ministers in Luxembourg.
"If the negotiations are serious I hope that we can find a solution that can be beneficial to the other side," said Larijani, according to the Mehr news agency.
However it remains to be seen what the outcome of the talks can be with Iran still insisting it has no intention of halting sensitive uranium enrichment operations, the key sticking point in the five-year standoff.
The United States and European Union have said negotiations can only start if Iran freezes enrichment. Tehran however says it will only negotiate with no preconditions and will never suspend enrichment.
The sensitivity of enriched uranium lies in the fact the substance can be used both to make nuclear fuel and, in highly enriched form, the explosive core of a nuclear bomb. Iran insists it only wants to produce civilian energy.
Iran has also upped the stakes in a standoff that has seen it slapped with two sets of UN sanctions, saying it has reached an "industrial scale" of enrichment and wants over 50,000 uranium-enriching centrifuges.
Larijani warned Solana not to insist on Iran suspending enrichment and come up with something new in the talks to recognise the progress claimed by Tehran on its nuclear programme.
"Solana should not talk about preconditions. New conditions mean there are new requirements and new initiatives should be presented," Larijani said, according to the Mehr news agency.
"Artificial views and diplomatic dancing in talks will have no result," added Larijani.
Iran’s foreign ministry spokesman Mohammad Ali Hosseini on Sunday gave the clearest possible indication Tehran would not budge on suspension, an idea he said was "definitely deleted from the literature of Iran’s nuclear activities."
President Mahmoud Ahmadinejad also showed he was in no mood for a suspension, saying in a television interview that such Western demands for a freeze were "not legal and political".
However Hosseini has also noted a softening of tone from Europe and even its arch enemy the United States in recent weeks, without specifying what statements he was referring to.
"The West and Europe have shown a softening with regards to the Islamic republic of Iran’s nuclear activities," Hosseini was quoted by the ISNA agency as saying on Monday.
"Larijani and Solana in their talks must clarify whether this is a new trick plan or not."
"After the second sanctions resolution the West has softened its tone towards Iran. I once again emphasise that the door of negotiation is open," he added.
The choice of Turkey as a venue, which Iranian media said came after intervention by Turkish Prime Minister Recep Tayyip Erdogan, is also set to fuel hopes that Ankara can help with mediation efforts between the two sides.
Solana and Larijani held several rounds of discussions last year which failed to find a solution to the crisis. They last met face-to-face for informal talks on the sidelines of a Munich security conference on February 11.