What is an example of a (compact) manifold which does not admit an atlas with all transition function between charts, polynomials? Of course any such example can not be an affine manifold.
It is observed by William M. Goldman that an affinely flat manifold (or just affine manifold) is a manifold with a distinguished coordinate atlas with locally affine coordinate changes:
http://www2.math.umd.edu/~wmg/MFO_Goldman.pdf
For an in-depth view of affine manifolds, see
Louis Auslander. The structure of complete locally affine manifolds