Treat it almost like an interview. Write up questions, think about the questions for a while, think about what a good and bad answer looks like. They're probably going to be pretty open ended, and the conversation may be somewhat circuitous, but they will be valuable.
Questions I like to ask are things like:
- Walk me through the process from ideation, spec, code, testing, deployment, maintenance. Who owns each part? How long does each part take? Which people/roles, processes, tools/tech are involved?
- If you left, what would you want to take from this team to your next? What does the team do better than others?
- What do you think the team needs to improve at? What does it do less well than other teams you've been a part of?
- How does change happen? What mechanisms do you have for change? Can you give some examples of change happening?
- How does the team feel about... Code Review (or anything else you care about)