Ok, so I put my Androids in a Group and let them bypass Pi-Hole. After a few minutes I could call them without a problem.
After acitvating Pi-Hole for them again, the calls get blocked again.
Now: thing is: I do have access to pihole.log, but: I have like 62 clients on pihole in my network and I'm struggling to fish out the one Android I'm trying to reach via WhatsApp-Call. I've got a few Router-Changes over the past weeks (don't ask), so I've got like 42 different IPv4/IPv6 adresses attached to the Androids. I just clicked on "flush network table" and I'm hoping I can resume digging into the logs later today...