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Chief entered English in the Middle English period through French chef and ultimately derives from Latin caput, “head.” Like captain, it can refer to the “head” of a group of people.
Etymology
From Middle English cheef, chef, from Old French chef, chief (“leader”), from Vulgar Latin capus, from Latin caput (“head”) (from which also captain, chieftain), from Proto-Italic *kaput, from Proto-Indo-European *káput. Doublet of cape (“point of land”), capo, caput, and chef through Latin (possibly also related to cape (“sleeveless garment”) and cap (“head covering”) from Latin cappa); doublet of head and Howth through Proto-Indo-European.