Antiferromagnetism and chemical ordering have both been previously suggested as causes of the observed semiconductorlike behavior in Cr3Al. Two films of Cr3Al(001)/MgO(001) were grown under different conditions to achieve different types of chemical ordering and electronic properties: one X-phase structure (semiconducting) and one C11b structure (metallic). The films were investigated by x-ray and neutron diffraction. Both films show commensurate antiferromagnetic order, with a high Néel temperature greater than 578 K, showing that the antiferromagnetism in Cr3Al is quite robust. Density-functional theory calculations were performed and it was shown that the well-known antiferromagnetic pseudogap in the density of states occurs for all types of chemical ordering considered. The conclusion of these studies is that the antiferromagnetism causes a pseudogap in the density of states, which is a necessary condition for the semiconductorlike transport behavior; however, that antiferromagnetism is seen in both metallic and semiconducting Cr3Al samples shows that antiferromagnetism is not a sufficient condition for semiconducting behavior. Chemical ordering is equally important.