Britain is giving an extra £5 million in non-lethal equipment to the Free Syrian Army.
The materiel includes radio and satellite equipment, as well as portable power generators.
Foreign Secretary William Hague said the assistance will not include weapons.
A Foreign Office spokesman said:
''As the Foreign Secretary says, we need to work with the Syrian opposition to ensure they prepare for the inevitable day of Assad's fall, including representatives of the Free Syria Army.
''We are therefore meeting political elements of the Free Syria Army.
''This is not taking sides in a civil war.''
The spokesman added:
''The risk of total disorder and a power vacuum in Syria is so great that we must build relationships now with those who may govern Syria in the future.
''If we do not work with those Syrians who want to see a democratic and open Syria, we leave a void to be exploited by al Qaeda and others with extremist agendas who wish to hijack the conflict.''
Also on Friday, the United States accused Hizbollah in Lebanon of providing "training, advice and extensive logistical support" to the Syrian regime.
Hezbollah is designated as a terrorist organisation by the United States and is under heavy sanctions.