Cr3Al shows semiconductor-like behavior which has been attributed to a combination of antiferromagnetism and chemical ordering of the Cr and Al atoms on the bcc sublattice. This article presents a detailed theoretical and experimental study of the chemical ordering in Cr3Al. Using density functional theory within the Korringa-Kohn-Rostoker (KKR) formalism, we consider five possible structures with the Cr3Al stoichiometry: a bcc solid solution, two-phase C11b Cr2Al+Cr, off-stoichiometric C11b Cr3Al, D03 Cr3Al, and X-phase Cr3Al. The calculations show that the chemically ordered, rhombohedrally distorted X-phase structure has the lowest energy of those considered and should, therefore, be the ground state found in nature, while the D03 structure has the highest energy and should not occur. While KKR calculations of the X phase indicate a pseudogap in the density of states, additional calculations using a full potential linear muffin-tin orbital approach and a plane-wave technique show a narrow band gap. Experimentally, thin films of Cr1−xAlx were grown and the concentration, growth temperature, and substrate were varied systematically. The peak resistivity (2400 μΩ-cm) is found for films with x=0.25, grown epitaxially on a 300 ∘C MgO substrate. At this x, a transition between nonmetallic and metallic behavior occurs at a growth temperature of about 400 ∘C, which is accompanied by a change in chemical ordering from X phase to C11b Cr3Al. These results clarify the range of possible structures for Cr3Al and the relationship between chemical ordering and electronic transport behavior.