Several dozen more residents of the town are in "danger of death" because of severe malnutrition, the humanitarian group warned.
The latest deaths bring the number of people reported to have died of starvation in Madaya to 46 since December, according to MSF.
Located in Damascus province, Madaya is under government siege, and its fate has been one of the sticking points for fresh peace talks on the Syrian conflict that opened on Friday after delays.
Madaya is one of four towns included in a rare deal last year that was intended to halt fighting and allow the entry of humanitarian aid.
But despite the deal, the UN and other aid groups have had only limited access to Madaya, along with rebel-held Zabadani, and the government-held towns of Fuaa and Kafraya, which are under opposition siege.
Conditions in Madaya have reportedly been among the worst, with about 42,000 civilians there surrounded by government troops who have laid mines around the town to prevent people leaving.
They have also called for the evacuation of those suffering malnutrition or sick with other illnesses.
Citing medics it supports in the town, MSF said there were at least 320 cases of malnutrition in the town, including 33 that were so severe that the individuals could die without prompt treatment.
"It is totally unacceptable that people continue to die from starvation, and that critical medical cases remain in the town when they should have been evacuated weeks ago," said MSF's director of operations Brice de le Vingne.
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