While some of the info is a little dated, and it is geared for the A330-200, there's a wealth of info on the Envoy suites (including a couple sitting together) in the following threads:
http://www.flyertalk.com/forum/us-ai...er-thread.html
http://www.flyertalk.com/forum/us-ai...er-thread.html
When I've flew in it, I didn't know until the day prior. It was switch/switch/switch for days, and when we got to the Envoy lounge the agents were trying to accommodate requests for sitting together.
In the end, on the way over, we ended up being on opposite sides (with windows), and given that you sleep most of the way, that worked out fine.