I would ask if they implement any of the ITIL processes, Joel sort of touched on it, but it's another set of IT best practices.
UPDATE: For example, I would ask about release and deployment management, and also incident management. This is important b/c not all software positions are at software companies, some are at organizations that just have software departments, in which the person hired would be working on software for the company. It would be nice to know there is a process in place whereby someone formally reports a bug and there's a process in place to get it fixed, and the fix is released with another process, possibly with other improvements, etc.
This is instead of someone emailing the developer directly and expecting a fix in an impossible time frame, which might be the way it's done at the interviewee's potential employer. Hearing about these processes in an interview would allow the candidate to seriously consider whether or not they want to be subjected to those practices.
Side note, looks like everyone who doesn't answer 'Joel Test' gets downvoted? Wow.