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This question already has an answer here:

How do I take the default off of my secondary Google Drive account, so my primary account shows up first in Google Drive?

marked as duplicate by serenesat, ale, user135384, Rubén, OnenOnlyWalter Jan 5 '18 at 17:19

This question has been asked before and already has an answer. If those answers do not fully address your question, please ask a new question.

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You can do the following.

  1. Log out from all Google accounts.
  2. Log in Google with the account that you want to use as primary first.
  3. Login with your secondary Google account (add account).
  4. Go to drive.google.com (It will be by default open with primary account). You can also switch account from there.

If you want to switch primary account of Drive, log out from all Google accounts and follow the above steps.

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