In the past, I did this in two ways: connecting all clients to a predefined host (simple, but requiring some client configuration) and having a host (or client) to translate their existence through "translation", address (for example, 10.0.255.255) (hard, firewalls / NAT can make life painful; clients do not need to be configured).
But yes, if WCF implements the discovery protocol, go with it. If he does what you want, he is probably better than anything you (or most people, for that matter) could write.
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