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Thrall is from the Old Norse þræll meaning a person who is in bondage or serfdom. The Old Norse term was loaned into late Old English, as þræl. The corresponding native term in Anglo-Saxon society was þeow (from Germanic *þewa-, "servant", from PIE *tek-, "to run") or esne (from Germanic *asniz, "reward", from PIE *osn- "harvest").
The English derivation thraldom is of High Medieval date. The verb to enthrall is of Early Modern origin (metaphorical use from the 1570s, literal use from 1610).