Electron-beam powder bed fusion (EPBF) has been demonstrated to enable crack-free additive manufacturing of the traditionally non-weldable IN738 Ni-based superalloy. This is related to grain boundary (GB) segregation and precipitation phenomena during EPBF thermal cycling. We investigate such GB microstructures around typical interphase boundaries in IN738. Cyclic reheating results in γʹ dissolution, reprecipitation, and formation of layers enriched in refractory elements at γʹ-γʹ interfaces. Interfacial excess shows that >10 atomic layers of Cr and 3.5 of Co at the GB suppress the segregation of W, B, and C. GBs around heterogeneously nucleated γ grains are decorated with less Cr and Co. This is linked to microsegregation of carbide and boride-forming elements, facilitating diffusion of minor elements during cooling. A heterogeneous interfacial excess profile at a γʹ-γʹ interface is reported. These findings improve the current understanding of interphase boundaries and segregation in EPBF-manufactured IN738, possibly contributing to crack-free additive manufacturing.