The highest MPG that I have ever seen is the Geo Metro XFI, at 53 MPG in the city and 58 MPG on the highway. Supposedly the Toyota Echo Spirit got 104 MPG, but it has never been proven.
Well it depends on what kind of car you are referring to. A normal non-hybrid car typically can get better than 30 or 40 mpg's. Hybrids however can get closer to 50. This could increase as technology improves.