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"Our goal is to convince our partners at the end of May, and if possible before.... If by chance there is a blockage by one or two countries, then France will take its responsibilities," Hollande said after talks on the first day of a European Union summit in Brussels.
"Political solutions have now failed (in Syria), despite every pressure," Hollande said. "We must go further because for two years there has been a clear willingness by Bashar al-Assad to use every means to hit at his own people."
France said earlier that Paris and London were pushing for the EU to drop the arms ban -- a move opposed by some European capitals who fear a flood of weapons into Syria will only escalate the conflict.
Berlin is known to be cool to the idea and on Thursday German Chancellor Angela Merkel said the EU needed to "proceed very cautiously" on lifting the embargo.
"If our partners in the European Union, in this case Britain and France, have a changed assessment of the situation, then the foreign ministers are of course ready to discuss this subject again," she said.
"But we have to be careful that the other side will not be provided with even more arms by countries that have another stance on Assad than Germany and the member states of the European Union," Merkel said.
Hollande insisted the rebels need to be armed to tip the balance against Assad's regime, which continues to "receive arms despite sanctions," notably from Russia.
"We must go further because there are threats, fears on the use of chemical weapons," Hollande added.
Some have also raised fears that European-supplied weapons would fall into the hands of radical Islamist militants, who are playing an increasingly prominent role in Syria's armed uprising.
But Hollande said Paris had "every guarantee that the weapons supplied will be in non-fundamentalist hands."
Hollande had upped the stakes on arrival at the summit, bluntly telling journalists: "We want Europeans to lift the arms embargo."
"We cannot allow a people to be massacred by a regime that for now does not want a political transition," Hollande said.
Sources said Hollande and British Prime Minister David Cameron held bilateral talks on Syria shortly before other EU leaders sat down and that the subject was to come up again on the second day of the summit on Friday, despite not being on the official agenda.
Paris and London are expected to press for quick new EU talks on the embargo, which was extended on February 28 for three months to June 1 by EU foreign ministers, though such sanctions are always reviewed in case events change.
At the February talks, ministers agreed to ease the embargo to enable any EU state to provide non-lethal aid or training to the insurgents. Britain quickly pledged armoured vehicles and protective clothing for the opposition.