Already (though without the gloss's definite article) in Hesychius epsilon6606, where Latte claims the headword as quoted from Homer, Iliad 22.438. Likewise also at the beginning of a more complex entry in Etymologicum Magnum 387.3, and, according to Adler, in the unedited Codex Laurentianus 59.16. (See also the scholia to Oppian, Halieutica 5.305, 599.) As comparanda Adler cites the unedited Ambrosian Lexicon (2196) and a scholium to Homer, Iliad 1.558 (where the accusative case occurs).
[1] Or: he who. Masculine nominative singular, in any event.