It's definitely not pointless asking technical questions. You probably have product-specific knowledge that he doesn't have, so if there's a specific area he should know about to work on your product, ask him about that.
Just because he's been working for 25 years doesn't mean he's a great programmer, anyway. It's very important to establish a lower bound in interviews, no matter what the resume looks like. Steve Yegge's five essential interview questions are a nice place to start for that and should apply to just about any programming job. (See here.)
There are also important soft skills to figure out. How will he fit with your team? What are his ambitions, both in this role and beyond? Is he ethical?
As far as time goes, it can vary depending on the nature of the interview, but an hour is my default. You should be able to make a plan for what you hope to learn about him and make that kind of evaluation within an hour (most of the time).