An EU official said Solana would meet Ali Larijani on Tuesday in the Italian capital.
Solana last met Larijani in June. His previous efforts to draw Tehran into negotiations on a package of inducements for it to suspend its uranium enrichment programme have failed so far to yield a breakthrough.
On Monday, the European Union instructed its experts to study further possible sanctions on Iran unless it halts activities the West suspects are aimed at making atomic bombs.
Iran denies it wants nuclear bombs, insisting its programme is aimed purely at generating electricity.
Solana’s talks with Larijani will follow a visit by Russian President Vladimir Putin to Tehran this week, which was watched closely because of Moscow’s possible leverage in the nuclear row.
Putin said on Thursday that direct dialogue was a better way of easing the crisis over Iran’s atomic programme than the threat of military force or sanctions.
Russia, a veto-wielding member of the U.N. Security Council, has been alarmed by the possibility that the United States might launch a military attack on Iran.
Putin has made clear to Washington that Russia would not accept military action against Iran. Putin has said he has seen no evidence that Tehran’s programme has military aims.
