Tell him to ask for the customs form at check-in and fill it in on the ground- will be much easier to do what with having to write down with passport and hotel details.
If he's in Chicago for a few days tell him - likely as you say he's there on business - to get a vetra card and load a pass onto it. He can do this at ORD. Tell him to eat the 5$ fee for getting the card - It's what I'm doing later this week as it looks like too much bother to get the card, register it and then load a pass / money onto it to get the 5$ back. I think there is a supplement to enter the 'L' Station at ORD but not to leave it.