Grain boundary (GB) glassy phase often results in poor ceramic performances. Here, a Multicomponent Grain Boundary Entropy (MGBE) descriptor extracted from high‐throughput first‐principle calculations is proposed to capture the nature of high‐entropy GB phases in ceramics. In a Si3N4 ceramic model system, MGBE is found to have a direct correlation with GB phase crystallinity, element segregation, and formation of pores. The predicted highest MGBE sintering additive combination (MgO‐Y2O3‐Er2O3‐Yb2O3) leads to high‐performance ceramics of homogenous microstructure and pure GB (YErYb)2Si3O3N4 phase without observable glassy film. Conversely, low MGBE additives result in a substantial amount of GB glassy phase, element segregation, and pore clusters. The MGBE descriptor can make a rapid screening of multicomponent sintering additives, offering a novel approach for rational designing of ceramics with targeted microstructure and performances.