How to Modify the Default Stroke Style?
How to Modify the Default Stroke Style?
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Based on your recording (the yellow warning sign at the bottom of the File New dialog), you are creating a CMYK document, with units in millimeters, but based on the Web profile (or another RGB one)! This means Ai would use the stroke defined in one of these screen-intended profiles, and not the one from Print-based ones.
Choose the proper document profile in the top row and set your settings for the new document anew — and the stroke alignment would be centered.If you really mean to change the stroke alignment for this particular (wrong) document profile — you can do it by actually opening the corresponding file (rather than creating a document based on it), and changing the Default Graphic Style.