UN peacekeeping spokesman Kieran Dwyer said the six observers had landed in the capital, Damascus, and would begin work on Monday.
The group left New York after the UN Security Council passed a resolution on Saturday, authorising their deployment.
Earlier, troops reportedly bombarded the restive city of Homs, straining the country's already fragile ceasefire.
The six are the first of 30 monitors approved for the observation mission, although UN and Arab League envoy Kofi Annan, who mediated the plan, hopes to eventually increase the number to over 200.
"The other monitors in the advance party are still expected in Syria in coming days," Mr Dwyer told AFP news agency.
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