strongly agree with Poisonous Apple:-)
In addition, when someone ask you, "ちょっといいですか?" while you look obviously free, it may imply that he or she wants to talk with you in person (not in public) by changing the place to have some private conversations.
Also you can use the phrase when you want to speak to (or get an attention of) a person who is doing something, talking with someone else, reading, etc...
In this case, it is the same as "May I interrupt you?"
In a closer relationship, you may use "ちょっといい?" or only "ちょっと・・・"