as far as i can remember, you can add a mirror to an existing vdev, but don't quote me on that quite yet. i'e been burned before with this old version of zfs we use...
testing in progress.... well that was fast.
#zpool create testMirror /mnt/storage/d1
#zpool attach testMirror /mnt/storage/d1 /mnt/storage/d2
basically, i create a pool, testMirror consisting of a single file, then i attach a new file to it, and here it is. it will take some time to resilver your data, it has to replicate everything onto the second disk.
Code:
pool: testMirror
state: ONLINE
scrub: resilver completed after 0h0m with 0 errors on Sat Jul 23 11:42:16 2011
config:
NAME STATE READ WRITE CKSUM
testMirror ONLINE 0 0 0
mirror ONLINE 0 0 0
/mnt/storage/d1 ONLINE 0 0 0
/mnt/storage/d2 ONLINE 0 0 0 73.5K resilvered
you'll have to export it through the gui, import it at the command line, add the mirror, allow it to resilver, export it, and re import it though the gui.
also note that this can only be done to top level disks and existing mirrors.