Hardmetals (or cemented carbides) were invented a hundred years ago and became one of the most important materials in engineering. The unique conjunction of fracture toughness, abrasion resistance and hardness makes WC-Co cemented carbides irreplaceable for numerous applications. As a rule, the WC crystallites in the sintered WC-Co hardmetals are perfectly faceted and possess a truncated trigonal prism shape. However, the so-called faceting–roughening phase transition can force the flat (faceted) surfaces or interfaces to become curved. In this review, we analyze how different factors can influence the (faceted) shape of WC crystallites in the cemented carbides. Among these factors are the modification of fabrication parameters of usual WC-Co cemented carbides; alloying of conventional cobalt binder using various metals; alloying of cobalt binder using nitrides, borides, carbides, silicides, oxides; and substitution of cobalt with other binders, including high entropy alloys (HEAs). The faceting–roughening phase transition of WC/binder interfaces and its influence on the properties of cemented carbides is also discussed. In particular, the increase in the hardness and fracture toughness of cemented carbides correlates with transition of WC crystallites from a faceted to a rounded shape.