When I open BW with the extension, it goes to Tab. How to open each time to Vault instead?
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Not sure what you mean by Tab, but to open the Web Vault you need to point your browser at https://vault.bitwarden.com/
The various ways of accessing Bitwarden are (largely) separate, they are accessing the same data but different applications.
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Why would you want that? The vault contains all items, which can be a huge list. Tab on the other hand only shows those items that match the current URL. If you do not get any hits under Tab then make sure to add URLs to your items.
Example:
Extensions shows 
, so I have an item with a matching URL.
Clicking the extension shows:
So I can either select this or - which is so much faster - press Ctrl + Shift + L to use those credentials to log into this forum.
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Why would you want to do that?
To save clicks and time. Why bother typing URLs or creating a Bookmarks collection when the Bitwarden extension can serve as a Bookmarks app that also logs you in? From the Bitwarden browser extension you can load a login page and complete the username and password from the extension Vault page favorites in one click: the Launch icon for the favorite. Cool! (Note: The extension has 5 “pages” selected from icons at the bottom: Card / Vault / Send / Generator / Settings)
But… every time you want to do that, clicking on the extension icon brings up the Card page, not the Vault page. The OP wants the Vault page to be the default, as do I.
Sure, you could log into Bitwarden and work from its browser tab, but the extension icon is always within easy reach.
This is no big deal, but it does mean one extra click dozens of times per day. It would be a nice option to have the extension default to the Vault page. (edited format)