Yep, it's dead easy: Stop the instance. Detach the root EBS volume. Attach the alternate EBS volume (as the root e.g. /dev/sda1) Start the instance.
This presupposes that your alternate EBS volume is bootable, of course - it has to contain the bootable OS image. Also, /dev/sda1 is the mount point for a Windows instance - check what it should be if you're doing this for a Linux VM.
1 This answer just saved my day! – Mr_Nizzle Sep 8 at 0:46.
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