The title "Most High" (hupsistos) comes from the Septuagint's translation of the Hebrew Elyon. It is first applied to Israel's God in Gen. 14:18,19,20,22, in connection with Melchizedek (cf. Heb. 7:1) and again in Num. 24:16 in connection with Balaam.
Moses uses it of Israel's God in Deut. 32:8 (cf. Acts 17:26). It is used several times in the Psalms (cf. Ps. 18:13; 78:35; 89:27) and a related title in Micah 6:6b.
This title for Deity (i.e., Elyon, see SPECIAL TOPIC: NAMES FOR DEITY, B.) is used several times in the NT.
For a good study of the use of Hebrew words in the NT, see Robert B. Girdlestone, Synonyms of the Old Testament. This term is briefly discussed on p. 35.
Please note that this title used of Israel's Deity does not imply the chief deity of a pantheon. It is a designation of monotheism in the Bible.
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