Yes, if your using PB.Net all the way through on both the client & WS side it should work.
I'm betting that the PB.Net side is a lot slower - especially the larger the result set buffers are, as the PB.Net Get/SetFullState is XML based. PB Classic's implementation is binary based, which should be significantly faster IMHO. However, I've never tested this theory.
FWIW: From the Appeon PB roadmap webinar this week, I don't see any future listed for PB.Net - so it looks like an EOL product to me. I'm wondering now if any further development in PB.Net would be prudent. Just my $0.02.
PS: WCF support in PB Classic is on the Appeon roadmap. :-)