Turns out it works fine out of the box if you have pkgconf installed.
root@freebsd-10:/ # pkg install -y pkgconf
Updating FreeBSD repository catalogue...
FreeBSD repository is up-to-date.
All repositories are up-to-date.
Checking integrity... done (0 conflicting)
The following 1 package(s) will be affected (of 0 checked):
New packages to be INSTALLED:
pkgconf: 0.9.12
The process will require 56 KiB more space.
[1/1] Installing pkgconf-0.9.12...
[1/1] Extracting pkgconf-0.9.12: 100%
root@freebsd-10:/ # gem install ruby-libvirt
Fetching: ruby-libvirt-0.5.2.gem (100%)
Building native extensions. This could take a while...
Successfully installed ruby-libvirt-0.5.2
Parsing documentation for ruby-libvirt-0.5.2
Installing ri documentation for ruby-libvirt-0.5.2
Done installing documentation for ruby-libvirt after 0 seconds
1 gem installed