Rising concerns on whether European weapons could end up in the hands of Islamic terror groups fighting alongside Syrian rebels prompted a change of heart among French leaders.
"At the moment, we do not have this guarantee," he said in an interview with France 2 news on Friday.
Instead, Paris will back a European Union embargo on all weapons shipments to opposition forces battling to overthrow Syrian President Bashar Assad.
Hollande's decision further splinters the already fractious support among Western powers to take a more direct role in ending the two-year Syrian civil war.
In Washington, President Obama is facing increasing pressure from Congress and members of his own national security team to escalate American involvement to support the rebels.
The administration has yet to act on recent recommendations by the National Security Council to provide body armor and other "non-lethal" equipment to rebel fighters.
On Capitol Hill, influential Democratic Sen. Carl LevinCarl Levin'Nuclear option' for Supreme Court nominees will damage Senate McCain's Supreme Court strategy leads to nuclear Senate The Fed and a return to banking simplicity MORE (Mich.) has joined GOP Sens. John McCainJohn McCainRepublicans tie Trump's Defense pick to funding fight Lawmakers haggle over funding bill as shutdown nears Markos Moulitsas: Kill the filibuster MORE (Ariz.) and Lindsey GrahamLindsey GrahamEx-Im Bank fails to get quorum reprieve in stopgap spending bill Overnight Defense: Funding bill would ease Trump Defense pick's confirmation | Obama delivers final security speech Congress wants hearing on Pentagon wasteful spending charges MORE (S.C.) in calling for U.S. air power to take out Assad's forces inside Syria.
Prior to Friday's announcement, French and British diplomats were actively pushing back against the embargo during a two-day summit of EU ministers in Dublin, Ireland, last week.
During the meeting, several EU ministers balked at directly arming the Syrian opposition over fear of the growing influence by militant Islamists within the rebel ranks.
"On one side you have to help and support people — on the other side prevent that aggressive weapons come into the wrong hands," German Foreign Minister Guido Westerwelle told Agence France Presse last Friday.
"The EU wasn't created to deliver arms. There can be no change to this principle," United Nations chief Ban Ki-Moon added.
Days after the Dublin meeting, NATO chief Anders Fogh Rasmussen said military action by the alliance against the Assad regime is not an option.
"We don't have any intention to intervene militarily in Syria," he said during a Monday speech in Brussels.
The White House remains dedicated to a political solution to ending the violence in Syria, but Obama has repeatedly stated that all options — including possible military action — remain on the table.