The first face-to-face talks between the Syrian government and the opposition - after nearly three years of civil war that have claimed more than 130,000 lives - were set to start Saturday, dpa reported.
Delegations representing the Syrian government and the opposition National Coalition were due to arrive at the UN headquarters in Geneva. Lead UN mediator Lakhdar Brahimi was to mediate, with talks expected to last through the end of the week.
According to Brahimi, the opening session will be devoted to "procedural matters."
The two parties were then scheduled to meet later Saturday to open up the first discussions on a host of issues, which could include the release of detainees and clearing the way for humanitarian aid convoys to reach towns and villages under siege.
The high-profile US- and Russia-backed talks have been touted by the international community as the last chance to bring an end to a spiraling conflict.
The future of the long-awaited talks was placed in doubt Friday when Damascus threatened to pull out after a disagreement about the agenda. That delayed the start of the direct talks a day, but Brahimi managed to bring both sides back to the table.
The Syrian government had insisted that the talks be devoted to "tackling terrorism" and refused to discuss a political transition in the country - a central point in a previous deal signed between the two sides in June 2012 and a precondition by the opposition for entering direct talks.
Weighting in from Tehran, Iranian President Hassan Rowhani noted that terrorism must first be brought under control before there can be hope for solving the Syrian crisis, the Iranian news agency Fars reported.
"You can't overcome the crisis in Syria with peace conferences. First you've got to get all parties to agree on the way to fight terrorism," he said. The next step would be creating a humanitarian corridor
Only after those two criteria have been reached, would the conditions be right for talks, said Rowhani.
The exclusion of Iran from the talks - demanded by the opposition - was criticized by various players in the negotiations this week.