Auger electron spectroscopy (AES) and secondary electron emission have been used to specify the room temperature monolayer adsorption characteristics of Re and Nb on the basal, polar surfaces of 4H–SiC. Measurement of the secondary electron emission current relates the absorbed crystal current to the change in AES peak-to-peak signal intensities for both substrate and adsorbate. For the 4H–SiC(0001) Si-face surface, both metals grow by formation of a single monolayer followed by growth of simultaneous monolayers. For the 4H–SiC(0001¯) C-face surface, both metals grow layer by layer (Frank–van der Merwe). Measurements of the coefficient of attenuation, inelastic mean free path, and coverage versus Auger intensities are also reported.