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I was playing Omega Ruby, and fighting Rich Boy Winston, and his Zigzagoon used Headbutt and it hit my Honedge. IF memory serves me right Headbutt is normal. It said that Headbutt was Not Very Effective. But it shouldn't have hit. So why did it??

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No Guard ensures that all attacks used by, and targeted at, the ability-bearer hit without fail.

Headbutt is Normal type, but it hit your Honedge because it had the ability No Guard.

EDIT:
As your comment below you have said that Scratch and Tackle do not have any effect on the Honedge, so, either I am misinterpreting how No Guard works, or the Zigzagoon used Scratch and Tackle and then used Odor Sleuth.
>Resets opponent's Evasiveness, Normal-type and Fighting-type attacks can now hit Ghosts, and Ghost-type attacks hit Normal.

It must have used Scratch and Tackle then used Odor Sleuth.
Hope I helped!
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Doesn't No Guard take into type effectiveness as well?
Things like Scratch and tackle have said it doesn't effect Honedge...
That has to be it!! Thanks!!! Probably just didn't motice odor sleuth.
Winston's zigzagoon does have odor sleuth
It does or the second or third rematch
It did on the first match rematches I don't know