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 LevinObama to preserve torture report in presidential papers 'Nuclear option' for Supreme Court nominees will damage Senate McCain's Supreme Court strategy leads to nuclear Senate MORE (Mich.) has joined GOP Sens. John McCainJohn McCainHillary Clinton under microscope at inauguration Tillerson met with top State official: report McCain ‘very concerned’ about Tillerson MORE (Ariz.) and Lindsey GrahamLindsey GrahamGraham: Trump would make mistake in not punishing Russia Graham to vote for Trump’s EPA pick Tillerson met with top State official: report 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.