Etymology
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pimento (n.)

1680s, pimiento (modern form from 1718), "dried, aromatic berries of an evergreen tree native to the West Indies," cultivated mostly in Jamaica, from Spanish pimiento "pepper-plant, green or red pepper," also pimienta "black pepper," from Late Latin pigmenta, plural of pigmentum "vegetable juice," from Latin pigmentum "pigment" (see pigment (n.)). So called because it added a dash of color to food or drink.

[I]n med.L. spiced drink, hence spice, pepper (generally), Sp. pimiento, Fr. piment are applied to Cayenne or Guinea pepper, capsicum; in Eng. the name has passed to allspice or Jamaica pepper. [OED]

The tree itself so called by 1756. The piece of red sweet pepper stuffed in a pitted olive so called from 1918, earlier pimiento (1901), from Spanish. French piment is from Spanish.

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Definitions of pimento

pimento (n.)
plant bearing large mild thick-walled usually bell-shaped fruits; the principal salad peppers;
Synonyms: sweet pepper / bell pepper / pimiento / paprika / sweet pepper plant / Capsicum annuum grossum
pimento (n.)
fully ripened sweet red pepper; usually cooked;
Synonyms: pimiento
From wordnet.princeton.edu