PiHole is connected to network and can see devices. Doesn't block ads

DHCP is for IPv4.
Have you checked for IPv6?
Other DNS servers (not Pi-holed) can be advertised through IPv6 routere advertisement.
On that Windows machine, what does below show when run in a CMD prompt?

netsh interface ipv6 show dnsservers

Are all those (if a couple of them) Pi-holed?