Used to describe the point furthest west in a geographic location, area or region. The westernmost point of France is the Pointe du Raz.
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Not for Directions
It's not used for giving directions in daily life, but for describing locations in a broader context. Alaska is the westernmost state in the whole United States.
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Relative Position
Implies comparison within a group; the term is relative to the other positions being discussed. Within the Canary Islands, El Hierro is the westernmost island.