Is it possible to add a fourth web.config transformation with Visual Studio?
I have three transformations:

But when I want to add one the option in contextual menu is disabled:

(It is in French, it means “Add Configuration transformations”)
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On the top of your screen where you change it from “Debug” to “Release” etc. Open the drop down, go to “Configuration Manager” in the “Active solution configuration:” list drop it down and select “New”.
When you’ve added the new one(s), you may need to refresh your project or close VS and re-open, then when you right-click a the web.config you will get the new configurations in the list.
Hope that makes sense. 🙂