The support page for Walkie Talkie has seemingly not been updated since before Focus modes became a thing. What exactly is the criteria? Is it hard coded only for Do Not Disturb and Theater?
Use Walkie-Talkie on your Apple Watch - Apple Support
Whether you’re out shopping or trying to find someone in a crowd, use the Walkie-Talkie app to get in touch with just a tap. Add friends, then manage when you want to talk.
support.apple.com
If you turn on Silent Mode in Control Center, you can still hear chimes and your friend's voice. If you turn on Theater Mode, it automatically makes you unavailable to talk with Walkie-Talkie. Do Not Disturb mirrors your iPhone settings, so you can manage which Walkie-Talkie alerts appear, and when.
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