As David Willis reports from Washington, President Obama had previously said proof of chemical weapons would be a "game-changer" in Syria
Syria has dismissed as "a caravan of lies" claims that it used chemical weapons, after the US said it would give the rebels "direct military aid".
President Obama made the decision after his administration concluded Syrian forces under Bashar al-Assad were using chemical weapons, a spokesman said.
A rebel leader, Salim Idris, told the BBC it was a "very important step".
But Syria's foreign ministry said the US had used "fabricated information" on chemical weapons to justify the move.
Washington was resorting to "cheap tactics" to justify Mr Obama's decision to arm the rebels, said a statement from the ministry.
On the ground, there were reports of the fiercest fighting in months in Syria's largest city, Aleppo.
Two years of conflict had killed at least 93,000 people, the UN said on Thursday, at a current rate of 5,000 people a month. More than 1,700 children under the age of 10 have died, it added.
CIA training?Ben Rhodes, a deputy national security adviser to Mr Obama, said the president had made the decision to increase assistance, including "military support", to the rebels' Supreme Military Council (SMC) and Syrian Opposition Coalition.
The US was "comfortable" working with Gen Idris, leader of the SMC, and aimed to isolate some of the more extremist elements of the opposition, such as Sunni militant group al-Nusra, he added.
Mr Rhodes did not give details about the military aid, other than to say it would be "different in scope and scale to what we have provided before".
Analysis
Initially US support looks likely to involve the supply of light arms and ammunition. Mr Rhodes says that the President has not made any decision to pursue a military option, like a no-fly zone, and he has ruled out the deployment of US ground troops. Requests from the opposition for anti-tank and anti-aircraft weapons are, we understand, still a matter of discussion.
Thus the US response to President Assad's apparent crossing of a "red line" seems tentative at best. As ever it raises more questions than answers.
Until now, the US has limited its help to rebel forces by providing rations and medical supplies.
Administration officials have been quoted by US media as saying it is most likely to include sending small arms and ammunition. The New York Times quoted US officials as saying Washington could provide anti-tank weapons.
The CIA is expected to co-ordinate delivery of the military equipment and train the rebel soldiers in how to use it, reports said.
Republican Senator John McCain, who has been outspoken in calls for arming the rebels, said he did not know to which type of arms the term "military aid" referred, but that he hoped for anti-tank weapons.
He said his greatest concern was the conflict "spiralling out of control because of a failure of American leadership".
In a BBC interview on Friday, Gen Idris said new weapons would help the rebels defeat the Assad regime and defend civilians.
Russian media on US position
State-controlled Channel One:
"One cannot but notice the unusual, not to say strange, format of the statement. First, it was a telephone conference. Second, Mr [Ben] Rhodes is a deputy national security adviser for strategic communications for the US president; he is of course across the subject, but his rank is rather low for such strong statements."
Rossiya 1 TV:
"One is instantly reminded of the well-known story with the vial with crushed chalk that Colin Powell presented as evidence of chemical weapons in Iraq. It is also interesting that the White House's statement came after Syrian rebels began suffering one defeat after another."
"We are in most need for anti-tank missiles and anti-aircraft missiles and in addition to all of that we need a huge amount of weapons and ammunition to stop the offensive of the regime," he added.
Prime Minister David Cameron said he shared the US view that the Syrian government had used chemical weapons, but that the UK had not yet decided whether to arm the rebels.
He told the BBC that engaging with moderate rebel groups - by working with them and providing training as well as technical assistance - helped limit the influence of more extremist fighters.
'Not convincing'The US intelligence community believes the Assad regime used chemical weapons, including the nerve agent sarin, on a small scale against the opposition on several occasions in the past year, said Mr Rhodes, adding that he estimated as many as 150 people had died in the attacks.
Washington's "clear" statement was welcomed by Nato Secretary General Anders Fogh Rasmussen, who urged Syria to let the UN "investigate all reports of chemical weapons use".
The US announcement is one the Syrian opposition has been pushing and praying for for months, says the BBC's Jim Muir in Beirut.
It seems clear Mr Obama has finally been persuaded, as Britain and France have argued, that the battlefield cannot be allowed to tilt strongly in the regime's favour, as is currently happening, says our correspondent.
Moscow said Washington's supposed evidence of chemical weapons use in Syria did "not look convincing".
UN Secretary General Ban Ki-moon's spokesman told the BBC he remained against "any further militarisation" of the conflict in Syria, saying the people there needed peace, not more weapons.
The support of the West's regional allies, Qatar and Saudi Arabia, had helped the rebels in the days after the uprising became militarised.
But the tide turned after the Assad regime turned to Moscow and Tehran for help. Hezbollah fighters from Lebanon have also been involved in the government's counter-offensive.
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