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Usually for a Van de Graf demonstration The person touching it has some level of electrical isolation from the ground. Be it their shoes or something else. If they were touching the ground directly or a piece of metal they would constantly be passing the electrons through and they wouldn't get that whole hair raising effect.
Okay, so you're insulated from ground. The generator charges you up. You are at the same charge as the generator. You let go of the generator. Why is there a potential difference?
If the generator is running, it's still adding more charge, so you will be instantly at different potentials
I see. Would there also be an arc if you put your hand near the generator while it was running, then?
As long as the potential is great enough to break down the dielectric of air yes.