I think its the way they're slotted. A Picatinny/MIL-STD-1913 rail has slots running horizontally, so that the rings can be solidly locked into specific spots. A Weaver rail doesn't, so you can stick the rings anywhere you want along the vertical part of the rail (vertically and horizontally looking at the top of the rail). I've got a flattop AR, but I've never tried sticking anything on it other than the carry handle, so I don't exactly know how it'd bolt up. The diamensions of the rings may be different by a few thousandths too, I can't remember.
-Quintin