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This is gen 8 VGC, rank battles.
The questions ask it all: Milotic or Blastoise?
I want to know some of the following:
In a meta game full of physical attackers such as Rillaboom and Cinderace, which one of the above can effectively check most of OU in SS?
Milotic has a niche ability with competitive, allowing it to pressure some dynamax moves and scare off intimidators. However, it’s lack of defense should be worrying. Is it still viable to go with Milotic still?
Blastoise on the other hand with a herb can be devestating (Shell+smash and Gigantamax has killed me so many time now). The one downfall for Blastoise is its lack of an efficient attacking stats, being 83 ATK. and 85 spAtk. However, it has relatively nice bulk and with its hidden ability, can be dominant in rain teams.
To the gist of things:
Rain team, Milotic or Blastoise?
Non-rain, Milotic or Blastoise?
It’d be nice if there could be movesets and EV spreads and justification and best teammates for each Pokémon. Thanks :>

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Short answer: Milotic
Better stat and good recovery movepool, could also be a succuessful psychical tank due to it could also learn coil and waterfall. Better Ability, also, if rainy team, why not a pokemon has the ability Swift swims and Rain dish and could learn Thunder and Hurricane?
Rillaboom is literally on every team and even with a +1 on Milotic and maxed investment...
252+ Atk Choice Band Rillaboom Wood Hammer vs. +1 252 HP / 252 Def Milotic in Grassy Terrain: 260-308 (128.7 - 152.4%) -- guaranteed OHKO
Though I do get it, Rillaboom is kind of an overkill which can be countered by Follow Me Togekiss. However, I'm just trying to say coil isn't enough to up its defense.
The post says you're playing VGC, but then it asks a question about OU. Which one are you playing?
I meant as in the OverUsed (Sword/Shield Metagame), not Smogon.  
Sorry for the misunderstanding.
So you're playing VGC? There is no such thing as OU without Smogon -- it's a Smogon format by definition.

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Best answer

Definitely Milotic, it got a much higher stat and good recovery movepool and toxic stall, suprisely, it could also use coil, dragon dance and hypnosis which means it could also be a psychical tank / sweeper.
If you said a rainy team, none of these two are good, I’ll suggest Swift Swim Chice Spes / Scarf Kingdra, it’s access to do more sweeping.
Saying of Raining team, Pelipper will also in, its ability drizzle helps a lot.
Milotic Set:
Milotic @ Leftovers
Ability: Competitive
Level: 50
EVs: 252 HP / 252 Def / 4 SpA
Bold Nature
IVs: 0 Atk
- Scald (Has a high chance to burned opponent, good power and perfect acc)
- Ice Beam (Cover)
- Recover (For good recovery)
- Haze (remove opponent’s. stat boost / lowered)
Simple set of mines, it works pretty well :)

Kingdra:
Kingdra @ Choice Specs
Ability: Swift Swim
Level: 50
EVs: 252 SpA / 4 SpD / 252 Spe
Modest Nature
IVs: 0 Atk
- Draco Meteor (High Pow, stab)
- Hydro Pump (Stab)
- Hurricane (Kill grass type, coverage)
- Flash Cannon (Kill ice type, coverage)
Strong, fast in rain, my best set I’ve used :)

Pelipper:
Pelipper @ Damp Rock
Ability: Drizzle
Level: 50
EVs: 252 HP / 4 SpA / 252 Spe
Timid Nature
- Hurricane (Stan, and why not)
- Scald / Ice beam (Two good move)
- Roost (Recovery move, lost flying type, which sometimes a good thing)
- U-turn (Switch for kingdra)
No need explain, right?

~Hope it helps!

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OP wasn't very clear about which format they're playing, but assuming they're playing VGC, these sets aren't very good. Politoed is favoured over Pelipper in VGC, and Milotic doesn't use moves like Scald and Haze nearly as often in doubles.
Thanks for the feedback, but this set actually works pretty well in all the format, which saves my team often, but also thanks about mentioning Politoad, I’ll edit it pretty soon.