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So if I use Psychium Z Psyshock, it will hit opponent on physical Defence or Special Defence?
Just curious.

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I would assume it hits specially, as it's no longer the move Psyshock, it's Shattered Psyche. I know Freeze-Dry doesn't hit Water types super effectively when it's Max Hailstorm, so it could be similar, but I don't have any definite proof for Psyshock.

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Special Defense.
Generally, Dynamaxed Moves and Z-Moves don't have the base damaging moves secondary effects.
Replay

The opposing Calyrex used Psyshock!
(Chansey lost 23% of its health!)

When using Shattered Psyche:

The opposing Calyrex surrounded itself with its Z-Power!
The opposing Calyrex unleashes its full-force Z-Move!
The opposing Calyrex used Shattered Psyche!
(Chansey lost 20% of its health!)

Therefore, Shattered Psyche uses the special defense of opposing target if it's special, and not using the base secondary effect of Psyshock.
It reflects similarly in Damage calculator also:

252 SpA Calyrex-Shadow Psyshock vs. 248 HP / 252+ Def Eviolite Chansey: 207-244 (29.4 - 34.7%) -- 8.9% chance to 3HKO
252 SpA Calyrex-Shadow Shattered Psyche (160 BP) vs. 248 HP / 252+ SpD Eviolite Chansey: 145-172 (20.6 - 24.4%) -- guaranteed 5HKO

Hope this helped!

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Thanks!
No problem.
Z-Moves in SwSh?
Nat Dex AG.