PokéBase - Pokémon Q&A
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Every time a Grotto regenerates, there is a 40% chance for a hidden item to spawn and a 40% chance for a visible item to spawn.

Items in all Grottoes

Visible items (all Grottoes)
Poke Ball: 12.5%
Great Ball: 5%
Ultra Ball: 2%
Potion: 6.25%
Super Potion: 2.5%
Hyper Potion: 1%
Repel: 6.25%
Super Repel: 2.5%
Max Repel: 1%

Hidden items (all Grottoes)
Damp Mulch: 6.25%
Growth Mulch: 6.25%
Stable Mulch: 6.25%
Gooey Mulch: 6.25%
TinyMushroom: 7.5%
Big Mushroom: 2.5%
Red Shard: 1%
Green Shard: 1%
Yellow Shard: 1%
Blue Shard: 1%
Rare Candy: 0.25%
PP Up: 0.5%
PP Max: 0.25%

Items in specific Grottoes

Routes 2, 3 (one), 5, 6 (one), 7, 9, 13, 18, 22, 23; Floccesy Ranch; Giant Chasm; Abundant Shrine (one); Lostlorn Forest; Pinwheel Forest (both)
Fire Stone: 0.25%
Water Stone: 0.25%
Thunderstone: 0.25%
Leaf Stone: 0.25%

Routes 6 (one), 13; Abundant Shrine (one)
Moon Stone: 0.25%
Sun Stone: 0.25%
Shiny Stone: 0.25%
Dusk Stone: 0.25%

Route 3 (one)
Dawn Stone: 1%

Hidden Grotto (Bulbapedia)

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First of all very small. Almost none because the items regen differently..
Also, different grottoes have different items sometimes available. Also, out of the 2% chance of regeneration, 40% are items, 40% are other items, and 20% are Pokemon. So the chances are small as the items will regenerate multiple times before all of the items are found. And the 2% chance is every 256 steps. VERY SMALL AMOUNT OF CHANCE OF GETTING ALL ITEMS IN A TIMELY MANNER.

Source: http://www.serebii.net/black2white2/hiddengrotto.shtml

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Can you give me an exact percentage
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The contents of the Hidden Grottoes are random, and if they are empty,foreach 256 steps, they have a 5% chance to regenerate, usually with different content than what was inside on the previous visit. Hidden Grottoes will not regenerate unless the items are obtained or the Pokémon are captured or defeated.

Source: Bulbapedia

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