According to the FCO, the aid is focusing on improving local communities' access to healthcare, water, energy and food.
British Foreign Secretary William Hague said in a statement that by making the contribution, Britain will be helping the Syrians with local governance and the delivery of basic services in order to meet needs on the ground.
The money will be donated to the Syria Recovery Trust Fund, a coordinated mechanism for donors to meet needs inside Syria, the FCO said.
Hague also stressed that a political settlement is the only way to end the violence and Britain will assist in any way it can.
This new funding will be used to repair damaged or destroyed infrastructure and restore services including water and sanitation, electricity, health and education, said Justine Greening, the British Secretary of State for International Development.