UN leader yesterday Ban Ki-moon said Iran had pledged in talks to play a "positive and constructive role" in efforts to end Syria's civil war.
But the Syrian National Coalition threatened to withdraw from the negotiations, due to start Wednesday in the Swiss town of Montreux, unless the invitation was retracted.
And the United States said Ban should withdraw the invitation unless Iran, a key backer of President Bashar al-Assad, gives "explicit" support to the conference aim of setting up a transitional government in Syria.
Ban told a news conference he extended a late invitation after intense talks over two days with Iranian Foreign Minister Mohammad Javad Zarif.
"Foreign Minister Zarif and I agree that the goal of the negotiations is to establish, by mutual consent, a transitional governing body with full executive powers," Ban told reporters.
"He assured me again and again that Iran, if they are invited, then they will play a very positive and constructive role," the UN secretary-general added.
Iran's involvement would mean all key countries linked to the worsening war will be among 40 nations at the opening of the peace conference.
Talks between Assad's government and the opposition are due to start in Geneva on Friday.
The Syrian National Coalition only decided on Saturday to attend the conference and reacted with fury to the UN's invitation.
Spokesman Louay Safi announced on the coalition's Twitter account that the opposition group would withdraw "unless Ban Ki-moon retracts Iran's invitation."
The threat came only hours after international leaders had hailed the coalition's decision to take part in negotiations.
The United States and other Western powers had opposed Iran's attendance at the meeting as long as it refused to accept a communique adopted by the major powers in Geneva on June 30, 2012, calling for a transitional government in Syria.
Washington made a new call for a clear signal from Tehran, a financial and military supporter of Assad, that it back efforts to set up a transitional government.
"The United States views the UN secretary general's invitation to Iran to attend the upcoming Geneva conference as conditioned on Iran's explicit and public support for the full implementation of the Geneva communique," US State Department spokeswoman Jen Psaki said in a statement.