PokéBase - Pokémon Q&A
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Single use ways:
Mable's Research Level 36: 10 Bottle Caps
Mable's Research Level 48: 3 Gold Bottle Caps
Side Mission 96: 2 Bottle Caps
Side Mission 103: 1 Gold Bottle Cap
There is a Bottle Cap in Wild Zone 20.

Repeatable Ways:
Infinite ZA Royale has a 6.9% chance to give you 3 Bottle Caps and a 3.45% chance to give you a Gold Bottle Cap after a Reward Match.

Ranked Matches:
1st place gives a 30% chance for 2 Bottle Caps and a 10% chance for 1 Gold Bottle Cap.
2nd place gives a 29% chance for 1 Bottle Cap and a 1% chance for a Gold Bottle Cap.

Sources: https://www.ign.com/wikis/pokemon-legends-z-a/All_Infinite_ZA_Royale_Rewards
https://www.eurogamer.net/pokemon-legends-z-a-bottle-caps#section-2
https://www.vice.com/en/article/pokemon-legends-z-a-patch-fixed-ranked-battles-with-rare-rewards-but-fans-arent-happy/

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As of Nov. 6th 2025, it's now possible to get bottle caps in ranked battles online. 1st place has a 30% chance of 2 bottle caps and a 10% chance of 1 gold bottle cap, and 2nd place has a 29% chance of 1 bottle cap and a 1% chance of 1 gold bottle cap. With the significantly improved odds + the shorter length of an online battle, I'd say this is way better than grinding the Infinite Z-A Royale... Well, as long as you're able to win <:)
Yes you are right, I will edit that in