The importance of structural effects on intergranular fracture is discussed in order to understand, predict and control fracture in polycrystals. The heterogeneity of fracture in a polycrystal has been found to be due to the difference in structure-dependent propensity to intergranular fracture among grain boundaries. The grain boundary character distribution (GBCD) which describes the type and frequency of grain boundaries is shown to be one of important microstructural factors affecting fracture processes and characteristics. A recent prediction of GBCD-controlled toughness and brittle-ductile transition is introduced. The importance of the connectivity of grain boundaries, the so-called grain boundary correlation number, is also discussed. Recent successful achievement of the control of intergranular brittleness is presented as an application of the result of basic research on fracture to the control of intergranular brittleness by grain boundary design and control in advanced materials.