They are different, as many a southerner would tell you. BUT you can make your own pimientos with red bell pepper, and in most cases no one would be the wiser. My great-grandmother, who makes the entire family a big batch of pimiento cheese every week, boils her red bell peppers, but I prefer to roast mine under the broiler. Then remove the skin and chop.
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Similar but, no, they're two different varieties of sweet pepper.