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Canonically it's definitely Iris and I'm a huge Misty fan.
However a hypothetical peak strength Misty if she had more fully evolved Pokemon and was in the Tournament would probably at least be capable of reaching Master's 8, if not beating Iris. Up until Champ Iris she had proven herself througout the series as Ash's most battle savvy companion, she smokes end of BW Iris.
Politoed and Mega Gyarados are both good but if this hypothetical has all her primary team members (except Psyduck probably) evolve, then she would have had Azumarill and Kingdra, both formidable against Iris specifically, plus her Starmie which could get a huge move upgrade needed with some boltbeam action or something.
And for hypothetical other members she'd probably also need something to cover the electric weakness this team has, I could see Quag or Lanturn, but I think it would be more interesting if she had a Lightningrod Seaking and it was like a weird dark horse.
