I would say no, because hairspray is water soluable and washes out of your hair, so it would the shoes too. And, the actual spray might damage your shoes.....or make them sticky.
No, I wouldn't do it. I've never sprayed suede shoes with it but I am certain that it would make the suede sticky and it would then collect dirt. I have bought weather proofing spray for suede shoes though but I have to say that I didn't think it worked too well.