Hello!
Yes, it works just fine.
You may want to combine it with Blokada Cloud:
This way you would be using the native Apple extension also for the ad-blocking feature, through all apps. We will launch the native Blokada app integration soon, for now you can configure it via app.blokada.org (Blokada 5 doesn’t have to be installed in this scenario).
I’m pretty confident that Blokada Cloud will work also in hot spot mode, if you configure the device(s) that connect through the hot spot to use it. There are no limitations on how many devices you can configure.
Please remember that the private relay does not protect traffic in other apps than Safari, it is not a full VPN service. To have full encryption throughout you would need to use Blokada Plus together with the WireGuard app or together with Blokada 5.