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Guard Lv. 5 already allows you to block truly ludicrous things such as a Rathalos' fireball or even the Nergigante's dive bomb attack.

There is however the set bonus of the Uragaan armor:

Uragaan Protection - Allows you to guard against ordinarily unblockable attacks.

What exactly is meant by an "ordinarily unblockable attack"?

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Beam or gas attacks are normally unblockable, but can be blocked with Guard Up. This includes:

  • Pukei-Pukei's poison cloud
  • Radobaan's and Uragaan's sleep clouds
  • Uragaan's fire cloud
  • Kirin's lightning attack that hits a long area across the ground
  • Teostra's supernova
  • Vaal Hazak's beam attacks
  • Xeno'jiiva's beam attacks
  • Kulve Taroth's lingering fire pools
  • Lunastra's fire puddles igniting from a different fire attack
  • Behemoth's ground shockwave

Additionally, some attacks can not be blocked even with Guard Up, such as:

  • Behemoth's horn impale
  • Behemoth's Ecliptic Meteor
  • Ancient Leshen's "bird nova", the attack that sends out Revoltures in all directions after charging up
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  • 1
    Do note that there are completely unblockable attacks even penetrates through Guard Up. Examples include Behemoth's horn grapple, and collaboration monsters' novas (Ecliptic Meteor, crow storm). – Arle Camille Nov 7 '19 at 13:14

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