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With the WooCommerce checkout integration you can subscribe emails during checkout. This feature is available in the free plugin. If you want to subscribe everyone on checkout you can set this integration to “implicit”, or otherwise you can show a checkbox during checkout to make it optional.
If you want to keep some data in sync between WordPress users and Mailchimp our Premium add-on has the UserSync feature for that.
Hope that helps. If you have any questions, please let me know!