Ps 99:6 Moses and Aaron were among his priests, Samuel also was among those who called upon his name. They called to the Lord, and he answered them. (ESV)
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It was the office of the priests to mediate between God and the Israelites, and to intercede on their behalf. Although Moses was not a member of the Aaronic priesthood, he exercised these priestly functions on such occasions as when the Israelites were fighting with Amalek (Exodus 17), when they sinned by worshipping the calf (Exodus 32; Deuteronomy 9), and when they murmured on the return of the spies (Numbers 14). I would say that this was what the Psalmist justifiably had in mind when referring to Moses as a priest.
The Pulpit Commentary says this about Psalm 99:6: "Moses and Aaron among his priests. Moses, though not called a priest in the Pentateuch, performed many priestly acts, such as sprinkling the blood of the covenant at Mount Sinai (Exodus 24:6-8), setting in order the tabernacle (Exodus 40:18-33)"--another source, the Quest Study Bible, says Moses served in the sanctuary (Exodus 40:22-27), consecrating Aaron and his sons (Leviticus 8:6-30), interceding for the people (Exodus 32:30-32; --just as a priest would-- and Numbers 14:13-19), etc. He is, therefore, not improperly, here included among God's priests. The priest's main job in the Old Testament was applying the blood of sacrifices and offering worship to God in the Tabernacle and Temple. --FSB (Faithlife Study Bible)
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