@Riot Tantram: Would it help to track punished players across multiple accounts if...
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the League Client kept a hidden/encrypted file somewhere in the program folder that held a unique identifier so that Riot could tell if a user was simply using multiple accounts from the same client?
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the League Client traced it's route to check if the connection is the same as that used by other accounts from the same location.
I believe that these techniques could be combined with existing profiling techniques used by Riot to match alternate accounts back to their owner. I believe they would help to ensure that punishments would stick instead of just forcing a player to play on their 'alt.'
Discuss in the comments, and feel free to share any other ideas you might have for how to address this issue.