Would this be possible? Applying for example an "overlay" blending mode to the fill of a shape while keeping the mode of the stroke set to normal? Or would I have to duplicate the shape?


Yes. Use the appearance panel (Window → Appearance).

Each stroke and fill has its own transparency options and you can add as many fills and strokes as you like, order them how you like and apply effects individually to whichever you like.

This, for example, is one shape:

enter image description here

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