Brahimi was set to meet separately with delegations from President Bashar al-Assad's regime and the opposition in Geneva before full talks resume tomorrow.
The UN-sponsored conference -- the biggest diplomatic effort yet to resolve Syria's devastating civil war -- opened in the Swiss town of Montreux yesterday with heated disagreements among the two sides and world powers.
Brahimi was set to first meet with opposition chief Ahmad Jarba yesterday afternoon and subsequently with the head of the Syrian regime's delegation, Foreign Minister Walid Muallem, the UN said.
"Do we go straight into one room and start discussing or do we talk a little bit more separately?... I don't know yet," Brahimi said.
Expectations are very low for a breakthrough at the conference, which officials have said could last up to 10 days, but diplomats believe that simply bringing the two sides together for the first time is a mark of some progress and could be an important first step.
Brahimi said he "had indications" from both sides that they were willing to discuss these issues.
Hadi Al-Bahra, a member of the opposition National Coalition's delegation, meanwhile told AFP the opposition felt it had benefitted from the regime's aggressive tone at the start of the conference yesterday.
"We have heard very positive feedback from inside Syria and it is the first time we've felt so much support from Syrians for the Coalition," Bahra said.
The regime delegation behaved "like the mafia, with a style very far from diplomacy," Bahra said.
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