On the user edit page the $profile variable is not set. Here is a patch to fix it. It need to be unserialized. See comment 1 for the patch.
This wasn't the case for me on a clean install. What are the steps to reproduce?
That is odd. All profiles have their settings unserialized when loaded by WysiwygProfileController, at the top of wysiwyg.module.
I would also like to know the steps to reproduce this, and if there are any modules enabled which interact with Wysiwyg.
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