The surfaces of four polycrystalline copper samples were examined under UHV conditions by AES: OFHC Cu, 99.99% Cu, 99.9999% Cu, and 0.086 wt. % Ag in OFHC Cu. Surface chemical compositions in the range of 25°–600°C were determined. Sulfur concentrations on the surfaces at various temperatures were also measured as a function of time. In almost all cases the sulfur concentration increased as (time)1/2. This process was interpreted in terms of a model based on diffusion controlled ’’outgassing’’ in which the sulfur segregated to the surface instead of vaporizing. The activation energies for this process for the four samples ranged from 0.18 to 0.31 eV/atom. RHEED data from an OFHC Cu sample indicated that sulfur formed an orthorhombic Cu2S structure on the surface. Around 500°C the Ag–Cu alloy experienced a complex, rapid stage of segregation of sulfur. Above this temperture range the surface sulfur concentration dropped rapidly, reaching zero at 600°C.