Is Volbeat worth a Master Ball?

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Probably not

Regional exclusive. It's not gone for good - just gated by geography rather than time, and solvable with a trip or a trade. You're probably better off saving the Master Ball for something rarer.

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Species info

Bug

Attack143

Defense166

Stamina163

Notable moves: Struggle Bug, Tackle, Infestation, Bug Buzz, Thunderbolt, Signal Beam