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Well first of all we don't actaully see the episode that they meet because they meet before the first episode. The story starts when ash was a kid. However, Jessie and James are adults. I could be wrong but I do believe they meet when join team rocket. You could Google the Pokemon episodes because I think the episode that has the exact time they join in the very first season. Hope I helped some.

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Q: Which episode do Jessie and James first meet?
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