Looking at the code for 5mins is the best start, if the code is really well organized and commented, there might not be any reason to talk to him at all.
If the code is hideous, well don't expect any intelligent reasons why he hacked something together, at best you can use him as a reference for some cruddy code and asks what's the purpose.
Either way, talking to the past developer is the least useful thing to do because either way, you're stuck with it now.