The UN-brokered negotiations in Geneva are the latest push by the international community to find a solution to Syria's five-year war, which has killed more than 270,000 people.
Both the government and the main opposition group, the Riyadh-based High Negotiations Committee, have agreed to attend the talks after the last round collapsed in February.
Chief opposition negotiator Mohammad Alloush and HNC delegation head Asaad al-Zoabi were in Geneva today, AFP correspondents in the Swiss city said.
The HNC has repeatedly called for Assad's departure at the start of any transitional period, but Syria's foreign minister said that was out of the question.
"We will not talk with anyone who wants to discuss the presidency... Bashar al-Assad is a red line," Walid Muallem told a Damascus news conference.
"If they continue with this approach, there's no reason for them to come to Geneva," Muallem said.
UN peace envoy Staffan de Mistura said the meetings in Geneva would not last more than 10 days.
The negotiations would cover the formation of a new government, a fresh constitution and UN-monitored presidential and parliamentary elections within 18 months, the envoy said.
However, Muallem said De Mistura had "no right" to discuss future presidential elections.
"Neither he nor anyone else, whoever they may be, has the right to discuss presidential elections," Muallem insisted.
"This right is exclusively for the Syrian people."
Muallem said the negotiations would aim to form a "unity government" which would then appoint a committee to either write a new constitution or amend the existing one.
The HNC has also insisted on Syria's territorial unity, but says talks must create a "transitional governance body with full executive powers".
Chief opposition negotiator Alloush said Muallem's comments were "ridiculous and show that the regime is not serious about the political process".
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