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Is the Grimoire used in the shooting phase or can it be used in any phase? The reason I'm curious is to whether it has to be used at a specific time or can be used before/after the psychic phase, depending on what powers you get off to maximize its effectiveness.

I believe grimoire is used in the movement phase (at any point). So you can try to use it then if it doesn't work, you can move.to a defensive position.