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There are 3 five-letter words beginning with OPI

OPINEopine v. (Intransitive, transitive) To have or express an opinion; to state as an opinion; to suppose, consider (that).
opine v. (Intransitive) To give one’s formal opinion (on or upon something).
opine n. (Biochemistry) Any of a class of organic compounds, derived from amino acids, found in some plant tumours.
OPINGoping v. Present participle of ope.
OPE v. to open.
OPIUMopium n. (Uncountable) A yellow-brown, addictive narcotic drug obtained from the dried juice of unripe pods of…
opium n. (By extension, countable) Anything that numbs or stupefies.
OPIUM n. an addictive narcotic.

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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