The food and other assistance will help 107,500 Syrians living in Rastan and nearby villages in the Homs region of western Syria, which has not received any aid since July.
Nearly six million Syrians live in hard-to-reach areas including one million people in besieged areas, according to the United Nations.
The deliveries, which require complex negotiations to ensure the security of the aid workers, were announced a day after UN aid chief Stephen O'Brien yesterday told the Security Council that the humanitarian crisis was worsening in Syria.
Three aid convoys recently sent to hard-to-reach areas were turned back at checkpoints manned by Syrian security forces or pro-government militias, he said.
A fourth aid delivery planned for rural Homs earlier this week was aborted due to delays and shelling in the rebel-held area.
The United Nations has deployed a vast humanitarian operation in Syria to come to the aid of some 13.5 million desperate people trapped in war, but the effort has faltered, in large part over the government's refusal to allow access.
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