The initial stages of interface formation between CaF2 and Si(111) have been studied with both core‐level and angle‐resolved valence band photoemission spectroscopy. Both the Si 2p and Ca 3p core levels indicate that a Si–Ca bond is present at the CaF2–Si(111) interface. Annealing of thin CaF2 films at 700–800 °C results in preferential evaporation of F, and the surface undergoes a number of reconstructions until a stable Si(111):Ca 3×1 reconstruction is obtained on which there is calcium, but no fluorine. This surface exhibits a surface state with an upward dispersion of 0.4 eV towards the K¯ point of the 1×1 surface Brillouin zone. Our results show that the CaF2 molecule can be dissociated on the Si(111) surface at typical epitaxial growth temperatures, with the Ca being more strongly adsorbed to the Si than is the F.