Through control of the grain-boundary structure, principally in the nature of the nanoscale intergranular films, a silicon carbide with a fracture toughness as high as 9.1 MPa.m1/2 has been developed by hot pressing β-SiC powder with aluminum, boron, and carbon additions (ABC-SiC). Central in this material development has been systematic transmission electron microscopy (TEM) and mechanical characterizations. In particular, atomic-resolution electron microscopy and nanoprobe composition quantification were combined in analyzing grain boundary structure and nanoscale structural features. Elongated SiC grains with 1 nm-wide amorphous intergranular films were believed to be responsible for the in situ toughening of this material, specifically by mechanisms of crack deflection and grain bridging. Two methods were found to be effective in modifying microstructure and optimizing mechanical performance. First, prescribed post-annealing treatments at temperatures between 1100 and 1500°C were seen to cause full crystallization of the amorphous intergranular films and to introduce uniformly dispersed nanoprecipitates within SiC matrix grains; in addition, lattice diffusion of aluminum at elevated temperatures was seen to alter grain-boundary composition. Second, adjusting the nominal content of sintering additives was also observed to change the grain morphology, the grain-boundary structure, and the phase composition of the ABC-SiC. In this regard, the roles of individual additives in developing boundary microstructures were identified; this was demonstrated to be critical in optimizing the mechanical properties, including fracture toughness and fatigue resistance at ambient and elevated temperatures, flexural strength, wear resistance, and creep resistance.