The recent discovery of topological insulators has revived interest in the band topology of insulators. In this Letter, we extend the topological classification of band structures to include certain crystal point group symmetry. We find a class of three-dimensional "topological crystalline insulators" which have metallic surface states with quadratic band degeneracy on high symmetry crystal surfaces. These topological crystalline insulators are the counterpart of topological insulators in materials without spin-orbit coupling. Their band structures are characterized by new topological invariants. We hope this work will enlarge the family of topological phases in band insulators and stimulate the search for them in real materials.