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No, when he picks the first painting, the odds is 5/94 = 0.053....= 5,3% then he picks 4 more :)

5.3% represents the 5 expensive paintings of the 100% paintings (94 cans).

It also represents picking 1 from the mix of 5 expensive and 89 cheap, that is the first pick! 5/94 is the odds of picking 1 expensive in the first pick out of 5 picks.
Every pick after pick 1 , will give higher odds, it is much higher !