Foreign Secretary William Hague will meet Syrian rebel leaders on Monday as Britain steps up pressure on President Bashar Assad's regime.
Talks will be held in London with representatives of the Syrian National Council and the National Co-ordination Committee for Democratic Change after months of behind-the-scenes diplomatic contact. Meetings will also be held in Downing Street with Prime Minister David Cameron's advisers.
The Foreign Office also announced that Frances Guy, former ambassador to Beirut, has been appointed as a full time envoy to lead work with exiled Syrian leaders.
A spokeswoman said: "We have been having regular contacts with a variety of figures in the Syrian opposition for several months. We are now intensifying these.
"The Foreign Secretary has appointed a senior foreign office official, Frances Guy, to lead this work and also intends to meet opposition representatives in the near future."
It comes amid heightened international pressure on Syria over the regime's brutal killing of more than 3,500 of its own people.
The Arab League formally suspended Damascus earlier this week, while France and Turkey called on the UN to ramp up sanctions.
Damascus has agreed "in principle" to allow an observer mission into the country amid a fresh wave of anti-government protests.
