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Spanish word quien comes from Proto-Indo-European *kʷe-, Proto-Indo-European *kʷo-, Proto-Indo-European *kʷ-, and later Proto-Italic *kʷoi (Who, what (relative, indefinite).)
*kʷe- (Proto-Indo-European)
*kʷo- (Proto-Indo-European)
*kʷ- (Proto-Indo-European)
*kʷey (Proto-Indo-European)
*kʷís (Proto-Indo-European)
Who, what (interrogative). Who, which, that (relative) Which, what.
*kʷoi (Proto-Italic)
Who, what (relative, indefinite).
*kʷis (Proto-Italic)
Who, what (interrogative).
quei (Old Latin)
(relative) who, what, that, which (interrogative) who, what, that, which.
qui (Latin)
(interrogative) who, what, which (relative) who, that, which.
quien (Spanish)
(construed with a) whom. Anyone; some people. Who. Whoever; whomever.