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If you use a Dusk Ball inside a cave, it will always be at its most effective catch rate. However, you need to use a Dusk Ball between 8pm and 3:59am outside caves to take advantage of its 4x catch rate. This is the game's night-time mode and Dusk Balls are more effective during this time.

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Q: What time are Dusk Balls effective in Pokemon Diamond?
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