From a thread in Brave’s community forums:
To bring back the Open as window option, go to
brave://flagsand set Shortcuts not Apps toDisabled. Once you do this, the option will appear again
I didn’t realize that this option was disabled by default in Brave and other Chromium-based browsers until I started setting up my Framework laptop. I found this thread, which had the solution.
➝ Source: community.brave.com

