The talks are brokered by Russia and Iran, which back the Syrian government, and Turkey which supports the rebels.
For the first time, the opposition delegation has been formed of representatives of armed Syrian rebels, but Jihadists such as Islamic State are excluded.
Kazakhstan's foreign ministry says it expects the talks, which have UN Syria envoy, Staffan de Misturto, in attendance, will come to an end by Tuesday.
Organisers have played down expectations of a breakthrough, and rebels say there will be no direct negotiations with the government.
The last round of talks between the opposition and the government, which were brokered by the UN, were suspended in early 2016.
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