Why can't I add Word to my most used list?

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I don't think you can. You can remove apps (maybe Word will appear if you remove 1 or 2 currently there) and change it so the list doesn't show at all. You can also replace the list with folders, i.e., Documents, (through Personalization\Start options), but I don't see a way to choose what appears in the most used list. How about just pinning Word to Start or the taskbar?
 
Why not add Word and /or Excel to the taskbar. If you often start working on a blank word document, Open Word 2016, go to File, go to Options, under the General tab, under the Start up tab, unclick the box : to show the startup screen when Word starts. When you start Word, it takes you to the blank document.