Small angle  twist boundaries and [001[(110) tilt boundaries in B-free and B-doped Ni-rich Ni3AI (76 at. pet. Ni) were examined using conventional electron microscopy techniques as well as annular dark field (ADF) imaging, X-ray Fluorescence (XRF) and spatially resolved electron energy loss spectroscopy (EELS) in an UHV scanning transmission electron microscope. The interface structure consists of periodically spaced pairs of a/2<10> partial dislocations, linked by an antiphase boundary (APB). An analysis of the separation of the partials gives APB energies which are lower than in bulk Ni3Al and which decrease with increasing misorientation angle. EELS, XRF and ADF imaging demonstrate that the APBs are Ni-rich. The observations on the APB chemistry and energy taken together lead to the conclusion that Ni-enrichment occurs to lower boundary energy by decreasing the number of high energy Al-Al bonds across the APB. These results on small angle boundaries lead to the suggestion that Ni-enrichment also occurs at large angle boundaries to decrease the number of high energy bonds across the interface.