Puritan settlers made only about 1,700 copies of The Bay Psalm Book in 1640, and just a handful of the hymnals have survived.
Two are owned by the Old South Church in Boston, where church elders have decided to auction one off to finance building repairs and the church's mission, ABC News said.
David Redden, vice chairman of Sotheby's auction house, which will sell the book this fall, called the opportunity an "earthquake" in the rare books world.
"It's going to be far and away the most expensive book ever sold," Redden said.
The last time a copy of The Bay Psalm Book was sold publicly it was purchased by Yale University in 1947 for $151,000.
Redden said this particular book is in excellent condition.
"One is so rare, no one could conceive of just owning one," Redden said. "It's the greatest rarity in the book world. Nothing is [as] desirable as The Bay Psalm Book."