The interactions of thin Ti layers deposited on the SiC(0001) √3 × √3 R30° surface at room temperature and after annealing at temperatures from 450 to 1200 °C was investigated using photoemission and LEED. Chemically shifted components were revealed in the Si 2p spectrum and found to be more intense and pronounced than the shifted component in the C 1s spectrum after Ti deposition and annealing. The relative intensity of these shifted components were found to increase initially upon annealing at temperatures up to around 700 °C. At temperatures above 800 °C only the shifted component in the C 1s spectrum remained which indicate that only TiC then remains on the surface. At annealing temperatures of 600–700 °C formation of the ternary Ti3SiC2 phase and an interface TiSix layer is suggested from shifts and relative intensities observed for these components. That the formation and decomposition of the ternary phase occurs at a considerably lower temperature than earlier reported is attributed to the fact that we investigated the interaction of considerably thinner Ti layers with SiC substrates than in those earlier reported studies.