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There are 5 five-letter words beginning with IO

IODICiodic adj. (Chemistry) of, or relating to iodine or its compounds, especially those in which it has a valency of five.
IODIC adj. pertaining to iodine, as applied to an acid.
IODIDiodid n. Archaic form of iodide.
IODID n. a salt of hydriodic acid, also IODIDE.
IODINiodin n. (Obsolete, US) Alternative form of iodine.
IODIN n. a chemical element, also IODINE.
IONICionic adj. (Chemistry) of, relating to, or containing ions.
Ionic adj. Synonym of Ionian; of or relating to Ionia or the Ionians.
Ionic adj. (Architecture) of an order of classical Greek architecture whose distinguishing feature is a capital…
IOTASiotas n. Plural of iota.
IOTAs n. Plural of IOTA.
IOTA n. (Greek) a Greek letter.

Scrabble words — in black are valid world wide — in RED are not valid in North America — in GREEN are valid only in North America.
Definitions are short excerpt from the WikWik.org and 1Word.ws.

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