Yes, fire ants do have venom. Unlike many other ants, which bite and then spray acid on the wound, fire ants bite only to get a grip and then sting (from the abdomen) and inject a toxic alkaloid venom called solenopsin, a compound from the class of piperidines.
Here is a link to a picture of a fire ant with its stinger:
and here is a picture of a fire ant actually biting for grip and then stinging:
http://www.alexanderwild.com/Ants/Making-a-Living/Tramps-and-Invaders/9549697_2t5e3/1/578630305_orJQA#578630305_orJQA
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