Metal-ceramic interfaces are scientifically interesting and technologically important. However, the transition of chemical bonding character from a metal to a nonoxide ceramic is not well understood. The effects of solute segregation and interfacial structural transitions are even more elusive. In this study, aberration-corrected electron microscopy is combined with atomic-resolution energy-dispersive x-ray and electron energy loss spectroscopy to investigate Ti-, V-, and Cr-segregated WC-Co interfaces as model systems. The experiments reveal the general anisotropic formation of reconstructed trilayer-like superstructures with segregant-specific compositional profiles that facilitate the transition from covalent to metallic electronic structures. Density functional theory calculations confirm the gradual increasing metallicity from WC to Co in the interfacial trilayers via increasing metallic solute concentration. This study uncovers unprecedented details of the sophisticated interfacial superstructures at metal-ceramic interfaces. It sheds light on how a metal transits to a ceramic at a "general" interface with strong segregation.