The deal struck between Kerry and Russian Foreign Minister Sergei Lavrov in Geneva on Friday agreed to a seven-day period of reduced violence and increased humanitarian aid deliveries.
If the truce holds, U.S. and Russian militaries would begin to coordinate air strikes against Nusra Front and Islamic State militants in an agreed area.
The plan aims to bring together the warring Syrian sides for talks on a political transition, which would involve Bashar al-Assad stepping aside.
"It’s a last chance to be able to hold Syria together," Kerry said in an interview with NPR’s Morning Edition. "If you fail to get a cessation in place now and we cannot get to the table, then the fighting is going to increase significantly."
He added: "What’s the alternative? The alternative is to allow us to go from 450,000 people who have been slaughtered to how many thousands more? That Aleppo gets completely overrun? That the Russians and Assad simply bomb indiscriminately for days to come and we sit there and do nothing?"
The five-year war has killed an estimated 430,000 people since the start of the conflict, with roughly 11 million people made homeless in the world’s worst refugee crisis.
Senior U.S. military and intelligence have criticized the plan saying Russia cannot be trusted. The plan envisions the U.S. military sharing targeting information for strikes against militants with Russian forces.
Kerry said the agreement had the support of U.S. President Barack Obama, with whom he met on Tuesday.
"Well, the president of the United States is ready and I think the military therefore will be ready," he said.
"Nobody’s asking people to abrogate our standards, but it is important for us to keep our part of the bargain," Kerry added.
The agreement marks the biggest test yet by Washington that it can work with Moscow to end a war that President Vladimir Putin transformed a year ago when he sent warplanes to join the fight on Assad’s side.
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