The coalition of political and armed opposition groups demanded the exclusion of other parties from the talks and a halt to the Syrian army's bombardment and sieges of populated areas.
It has appointed Mohammed Alloush, a political leader of as the Saudi-backed armed group Jaish al-Islam, as its chief negotiator, the coalition's general coordinator, Riad Hijab, announced at a news conference in Riyadh.
He said Asaad al-Zobi, a general who defected from the army, will serve under Alloush as head of the delegation, with Syrian National Council chief George Sabra as his deputy.
Hijab insisted the committee's delegation should be the only opposition representative at the talks, aimed at bringing an end to a five-year-conflict that has cost more than 260,000 lives.
"We will not go to negotiations if a third party or person is added," he warned.
Hijab also said that "we cannot go to negotiations with our people dying of hunger and under shelling" by pro-regime forces.
Countries pushing for a peace deal for Syria, including the United States, Russia, Saudi Arabia and Iran, have struggled to agree on the list of opposition delegates.
Saudi Foreign Minister Adel al-Jubeir said yesterday that the Riyadh-based committee was "the concerned body, and nobody else can impose on them who should represent them" in negotiations.
Riyadh in December brought together about 100 representatives at the meeting of Syria's main political opposition and armed factions.
They agreed to negotiate with the regime but insisted Assad step down at the start of any political transition.
The Islamic State jihadist group, which has seized large parts of Syria and Iraq, and the Al-Qaeda affiliated Al-Nusra Front were excluded from the Riyadh meeting.
A newly formed secular Kurdish-Arab alliance, the Syrian Democratic Council, last week demanded its own seat at the negotiating table and said it would not be grouped with the Riyadh body.
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