I can see that the Mac's operation will be different, and I can understand that these are two different 'open with' mechanisms. However ....
Looking at Sigil from new users' viewpoints, I'm afraid they will also be surprised that a right-click on an xhtml file in the Browser doesn't immediately offer the tool they took trouble to specify in Preferences, especially if they have a limited set of Toolbars visible to reduce clutter.
Not a major worry for me.