The atomic structure of the Σ=5 [001] (310) grain boundary in NiAl was examined by high resolution electron microscopy and multislice image simulation. As in most other intermetallic compounds, the grain boundaries in NiAl are intrinsically brittle at low temperatures. Although there have been few studies on this alloy, the energies of NiAl grain boundaries have been calculated using embedded atom potentials for both stoichiometric and non-stoichiometric structures. These studies are consistent with the results of Bradley and Taylor, which indicate that nickel-rich compositions result from nickel antisite defects on the aluminum sublattice, while aluminum-rich compositions produce constitutional vacancies on the nickel sublattice, and with recent field ion microscopy results on nickel-rich alloys.The Σ=5 grain boundary was prepared by diffusion bonding at 1000 °C. A JEOL 4000EX was used for HREM imaging and the NUMIS multislice simulation program was used to simulated images. Analysis of these images considered the effects of grain boundary expansion, rigid body displacements along the boundary, grain boundary stoichiometry, and point defects at the boundary.