Can I make my Pihole have 2 valid IP addresses for DNS?

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If you can't use local IP's for DNS on your router, this may be due to DNS rebind protection on the router:

Why won't Pi-hole work with DNS rebind protection enabled?

What is DNS rebind protection? If your router has an option called DNS rebind protection enabled, you may run into issues when trying to use Pi-hole as your DNS server. The reasons for this are quite technical, but to summarize what this option does in one sentence: DNS rebind protection does not allow DNS queries to be answered with a local IP address. Why does this interfere with Pi-hole? DNS rebind is meant to be a countermeasure to an attack on your network. So in many cases, it's actu…

If you cannot disable this on the router, then your best approach is to disable DHCP on the router, and use the Pi-hole DHCP server.

How do I use Pi-hole's built in DHCP server (and why would I want to)?

Using Your Existing Router For Network-wide Ad Blocking You might not need to use Pi-hole's DHCP server: In many home environments, your router also functions as your DHCP server. In this case, you can often set Pi-hole to be the DNS server for your network clients in the router's DHCP (or LAN) settings page, which allows all of your network clients to block ads simply by connecting to the network. Setting it up this way is also what makes Pi-hole very powerful for network-wide ad blocking. …

What make and model router are you using?