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I’ve seen this happen when the group settings and tax rules look fine but the price display mode isn’t synced. In the Customer Groups page, double check that the B2B group is set to show prices tax excluded, then clear all caches, including Smarty. Sometimes you need to resave the tax rule too. I ran into the same thing while browsing tips on https://www.b2b.blackfriday/ and that combo fixed it on my setup.
Edit History
Jumping in on this older post because I’ve seen similar issues in 8.2. One thing worth checking is whether the B2B group has “Display tax in cart” disabled in the group settings; sometimes that overrides tax rules. Also, make sure the 0 percent rule is the only one matching the customer’s country. If anyone found a clean workaround or patch for this, I’d love to hear it too.