Grain boundary engineering (GBE) is considered to be an attractive approach to microstructure control, which significantly enhances the grain-boundary-related properties of face-centered cubic (FCC) metals. During the twinning-related GBE, the microstructures are characterized as abundant special twin boundaries that sufficiently disrupt the connectivity of the random boundary network. However, controlling the grain boundary character distribution (GBCD) is an extremely difficult issue, as it strongly depends on diverse processing parameters. This article provides a comprehensive review of controlling GBCD during the twinning-related GBE of FCC materials. To commence, this review elaborates on the theory of twinning-related GBE, the microscopic mechanisms used in the optimization of GBCD, and the optimization objectives of GBCD. Aiming to achieve control over the GBCD, the influence of the initial microstructure, thermo-mechanical processing (TMP) routes, and thermal deformation parameters on the twinning-related microstructures and associated evolution mechanisms are discussed thoroughly. Especially, the development of twinning-related kinetics models for predicting the evolution of twin density is highlighted. Furthermore, this review addresses the applications of twinning-related GBE in enhancing the mechanical properties and corrosion resistance of FCC materials. Finally, future prospects in terms of controlling the GBCD during twinning-related GBE are proposed. This study will contribute to optimizing the GBCD and designing GBE routes for better grain-boundary-related properties in terms of FCC materials.