"If the opposition does not participate there will be no Geneva conference," Brahimi said at a news conference in Damascus before returning to Beirut as part of a regional tour to try to garner support for the US and Russian backed peace initiative.
"The participation of the opposition is essential, necessary and important," the veteran Algerian diplomat said, adding the proposed conference was intended "to help the Syrians and resolve their problems".
Brahimi, who met with President Bashar al-Assad on Wednesday, said "the Syrian government has agreed to participate in Geneva".
"The opposition, whether the National Coalition or others,are trying to find a way to be represented," he said, referring to the main opposition bloc.
The renewed bid for peace talks aimed at resolving the twoand a half-year conflict comes after last month's US-Russian accord on dismantling Syria's chemical arsenal.
But Syria's increasingly divided opposition has thus far balked, with the National Coalition saying it will not take part in the so-called Geneva II process if Assad's resignation is not on the table, a demand rejected by Damascus.
Powerful rebel groups on the ground have meanwhile denied the Coalition represents them, and some Islamist brigades have warned any Syrians taking part in the talks would be viewed as traitors.
The Coalition, which is under pressure from its Western and Arab backers to attend Geneva II, is to meet on November 9 to decide whether to participate.
The civil war, which erupted after a fierce government crackdown on Arab Spring-inspired protests in March 2011, has claimed an estimated 120,000 lives and forced millions to flee their homes.
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