Early reports suggest it has largely been respected by both sides of the conflict since it began on the stroke of midnight (2200 GMT).
Monitoring group the Syrian Observatory for Human Rights (SOHR) said it was quiet in the north of Latakia province and in the central provinces of Homs and Hama.
However one rebel commander told the Reuters news agency Government shelling was still taking place in some areas.
Fares Bayoush, head of the Fursan al-Haqq rebel group which fights under the banner of the Free Syrian Army, warned that continuing violations could lead to a collapse in the agreement.
Members of the so-called Islamic State group have also reportedly stormed a northern border town captured by Kurdish fighters several months ago, prompting an outbreak of fighting.
They have also claimed responsibility for a car bomb attack east of Hama city, which killed two people and wounded several others.
Brokered by the US and Russia, the ceasefire is the first major cessation of hostilities since 2011 when the civil war that has claimed more than 270,000 lives began.
It is designed to allow aid to reach civilians and to pave the way for peace talks to resume.
Russia, which has been propping up the Syrian government with airstrikes, has vowed to keep up its bombing campaign against terrorist groups not covered by the truce, including so-called Islamic State and al Nusra Front.
However it said it would halt airstrikes for the day on Saturday to ensure no wrong targets were hit by mistake.
To avoid any possible mistakes when carrying out strikes, Russian military planes, including long-range aviation, are not carrying out any flights over Syrian territory on 27 February," the defence ministry said.
The UN Security Council has given its unanimous backing to the cessation of hostilities in a resolution drafted by the US and Russia.
It called on all the parties concerned to observe the terms of the agreement and "fulfil their commitments".
US ambassador Samantha Power acknowledged there was "some scepticism" as to whether the ceasefire would last, but said it offered the "best chance to reduce the violence".
Dozens of Syria's opposition and rebel groups said they would abide by the deal.
The Syrian regime has said it will abide by it but retains the right to retaliate for any attacks.
A previous agreement was due to come in to force last Friday but appeared not to have been observed by some groups.
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