iPhone remote app
How do you unpair an Apple TV from a iPhone remote?
iPhone 13 Pro
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The software remote detects available Apple TV boxes in real time, regardless of pairing.
Set up the Apple TV Remote on your iPhone or iPad - Apple Support
If an iPhone is paired with an Apple TV box, then you can remove that pairing from: Apple TV: Settings﹥Remotes and Devices﹥Remote App and Devices﹥[select iPhone]﹥Forget This Device.