The cold-cathode electron emission properties of amorphous tetrahedral diamondlike carbon are promising for flat-panel display and vacuum microelectronics technologies. The onset of electron emission is, typically, preceded by “conditioning” where the material is stressed by an applied electric field. To simulate conditioning and assess its effect, we combined the spatially localized field and current of a scanning tunneling microscope tip with high-spatial-resolution characterization. Scanning force microscopy shows that conditioning alters surface morphology and electronic structure. Spatially resolved electron-energy-loss spectroscopy indicates that the predominant bonding configuration changes from predominantly fourfold to threefold coordination.