But the delegation will not join the talks until Wednesday, after two days of preliminary discussions among opposition participants, the Al-Watan newspaper reported.
Ahmed Arnus, a top adviser of Foreign Minister Walid Muallem, will be among six other members of the delegation.
"Opposition figures will meet together from Monday before the Syrian Arab Republic delegation joins them on Wednesday," the paper said.
"It is a consultative meeting to prepare the ground for a dialogue which will be held later in Moscow or Damascus."
The main exiled opposition alliance, the National Coalition, has announced it will not attend the Moscow talks, although some of its members are attending in a personal capacity.
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"Any talks should be held in a neutral country and overseen by the United Nations," a Coalition source said, alluding to Moscow's strong support for the Damascus government.
Five Coalition members, including Ahmed Jarba, a former leader seen as close to Saudi Arabia, are attending in a personal capacity.
Members of opposition groups tolerated by the Damascus authorities are also travelling to Moscow.
Washington has given the talks its backing although it has said it is up to the opposition whether to attend.
"We've certainly conveyed we'd support them attending the meetings," State Department spokeswoman Jen Psaki said.
Russian Foreign Minister Sergei Lavrov has expressed hope that the meetings will help the UN envoy for Syria, Staffan de Mistura, organise a new peace conference to negotiate a way out of the civil war that has claimed more than 200,000 lives since 2011.
Two previous rounds of talks in Geneva ended without success.