The Kazakhstan talks are brokered by Russian Federation and Turkey, which back opposing sides in the almost six-year war and have taken the lead with peace efforts since December.
Earlier on Tuesday, Kairat Abdrakhmanov, Kazakhstan's foreign minister said the talks would focus on mechanisms to monitor Syria's ceasefire and to hold violators accountable.
The two-day conference is aimed at bolstering a December 30 cease-fire ahead of the United Nations talks slated to begin February 23.
Disputes over the agenda have helped to torpedo previous rounds of Syria peace talks.
Russian Federation and Iran, close allies of President Bashar Assad, and Turkey, which backs the rebels, previously pledged to enforce the cease-fire, but both sides have alleged repeated violations.
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Bilateral talks between participants of the Astana Process on Syrian Settlement has kicked off in the Kazakh capital, Kazinform correspondent has learnt from a source close to the organizers of the talks.
De Mistura says the talks will be in line with UN Security Council Resolution 2254 aimed at ending the conflict in the Arab country.
Muslit, however, said the opposition had yet to receive an agenda for the upcoming negotiations. The Syrian government said on February 13 it was ready to agree on prisoner swaps with rebel groups.
"A second worldwide meeting on Syria is due in Astana these days", Zakharova said.
Rebels will send the same delegation to Thursday's talks, headed by Mohammad Alloush of the Islam Army rebel group. Jordan will also be represented by a "high-level delegation", government spokesman Mohamed Momani said.