As we said in our review, The Legend of Zelda: Breath of the Wild makes better use of Amiibo than any other Nintendo game to-date.
To use Amiibos, you’ll need to wait until you get the Amiibo Rune. You can then use absolutely any Amiibo in any open-area of the game. You’ll also need to turn the functions on in the options setting of the game. It’s also worth noting that you can use these once a day.