The formation of a carbide interface layer between the Si͑100͒ surface and hydrogen-free sp 2 amorphous carbon films is investigated at different substrate temperatures in the range from ambient to 1040°C. The analysis of the interface and film is performed with photoelectron spectroscopy in the ultraviolet and x-ray regime. A carbon beam is created by electron-beam evaporation of graphite and the stepwise in situ deposition of carbon ͑0.3 monolayer/min͒ allows to follow the evolution of the carbide surface layer and interface. At temperatures at and below 750°C a thin carbide layer ͑р0.4 nm͒ is rapidly formed, followed by the growth of a pure carbon overlayer. The valence band ͑VB͒ as well as the core-level spectra reflect the rapid formation of a SiC interface and subsequent carbon overlayer growth. If a substrate temperature above 900°C is chosen, the carbon overlayer growth is completely suppressed, and a pure carbide layer is present. The VB spectra of the carbide layer are identical to those of the bulk SiC phases. The continued carbide layer formation and absence of a carbon overlayer is attributable to the enhanced outdiffusion of silicon, which leads at the same time to the formation of a Si-rich surface. For temperatures below 900°C the carbidic interface is carbon-rich, which is attributed to carbon enrichment at the carbon-overlayer-carbide contact area. A comparison with experiments described in the literature allows to evaluate the influence of processing parameters such as ion irradiation on the interface formation.