Pokemon Brilliant Diamond & Shining Pearl adds in several ways to get the National Dex Pokemon, but obtaining some of them is always going to be a bit harder than the others. Porygon has always been a Pokemon that is harder to get in games, and Brilliant Diamond and Shining Pearl are no exception to this rule.
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There is only one way to capture a Porygon in the game, and it's going to take a lot of work to
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