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chief (adj.)

c. 1300, "highest in rank or power; most important or prominent; supreme, best, placed above the rest," from Old French chief "chief, principal, first" (10c., Modern French chef), from Vulgar Latin *capum (also source of Spanish and Portuguese cabo, Italian capo, Provençal cap), from Latin caput "head," also "leader, guide, chief person; summit; capital city" (from PIE root *kaput- "head").

chief (n.)

c. 1300, "head, leader, captain; the principal or most important part of anything;" from Old French chief "leader, ruler, head" of something, "capital city" (10c., Modern French chef), from Vulgar Latin *capum, from Latin caput "head," also "leader, chief person; summit; capital city" (from PIE root *kaput- "head"). Meaning "head of a clan" is from 1570s; later extended to headmen of American Indian tribes (by 1713; William Penn, 1680s, called them kings). Commander-in-chief attested from 1660s.

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Definitions of chief from WordNet
1
chief (n.)
a person who is in charge;
Synonyms: head / top dog
chief (n.)
a person who exercises control over workers;
Synonyms: foreman / gaffer / honcho / boss
chief (n.)
the head of a tribe or clan;
Synonyms: headman / tribal chief / chieftain
2
chief (adj.)
most important element;
the chief aim of living
Synonyms: main / primary / principal / master
From wordnet.princeton.edu