The first European explorer known to have sailed up the St. Lawrence River itself was Jacques Cartier. At that time, the land along the river was inhabited by the St. Lawrence Iroquoians. Because Cartier arrived in the estuary on Saint Lawrence's feast day of August 10th, 1535, he named it the Gulf of Saint Lawrence and the St. Lawrence River.
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LibriVox: Mariner of St. Malo, A Chronicle of the Voyages of Jacques Cartier by S. Leacock, read by R. Cotter

348. Christian Discoverer of Canada
10:43

347. God, Diamonds, and Baptisms
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346. Holy Riverbank Cross
17:07