The former Prime Minister is supporting a scheme to run "split shifts" in schools in Lebanon, where hundreds of thousands of Syrian refugees have fled.
Advocates of the proposals argue they would allow youngsters to get back into school within weeks.
The plan has the support of more than 50 campaign groups and international organisations as well as UN Secretary General Ban Ki-moon and children's education campaigner Malala Yousafzai.
Mr Brown, MP for Kirkcaldy and Cowdenbeath and a United Nations special envoy for global education, will tell MPs today: "It was through the creation of the Red Cross and later Medicine San Frontieres that the right to healthcare, even in conflict, has become the norm over a century.
"By fighting for the fundamental right to education for the children of Syria we can establish the principle that even in the most hopeless of situations learning can continue."
The Lebanese Government and non-governmental organisations are already offering schooling to thousands of refugee children.
However, a lack of funding means they are unable to reach the hundreds of thousands more.
Najib Asmi Mikat, Prime Minister of Lebanon, said he reiterated his support for the initiative "which represents an important step to ensuring a generation of children does not miss out on education".