Step 1. Become filthy rich. Step 2. Cultivate friends who are members of Augusta National. Step 3. Shmooze heavily. There are a few other ways. Dwight Eisenhower was able to play Augusta because he was a war hero and President. To follow that route, ask your Congressman to appoint you to West Point, study hard, and hope for another World War just as your career is reaching its peak. Simply being President doesn't seem to be enough. I don't think they ever invited Bill Clinton to play. Seriously, Augusta is incredibly exclusive and snobbish. Asking won't get you much of anywhere.
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I called Augusta National at 706-667-6000 and connected with a receptionist. She transferred me to HR who then transferred me to the ANGC job line. The second option allows you to leave you name and address, so they can mail an application to you if you live outside the area. In you are in or near Augusta, you can go to a designated location on 3 dates in January to apply in person (they provide the address in the message). I have read where it is impossible unless you know someone to be accepted. I am happy just to have an application coming my way.
After calling Augusta National I was told that you had to know someone who already volunteered at the Masters to put your name in the hat for future volunteer.
You can't play at Augusta National unless you are the guest of a member or you qualify for The Masters.