Re: Single Big Bet - Highest Winning %.
Tell him to bet the don't pass line on a craps table. This is not (necessarily) a one roll bet so it may take a little time to see his end result. If he wants guaranteed instant gratification find a craps table with the field payout where 12 (boxcars) pays triple and 2 (snake eyes) pays at least double (a very few tables have both 12 and 2 paying triple). Both these bets are better than red/black on a roulette wheel even if you found a European wheel with just a single zero.
Just as an added note, there will be no table game in Vegas where he has a positive edge like you described.
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