The growth of ultrathin ZrO 2 films on Si(1 0 0)-(2 × 1) and Si(1 1 1)-(7 × 7) has been studied with core level photoelectron spectroscopy and X-ray absorption spectroscopy. The films were deposited sequentially by chemical vapor deposition in ultra-high vacuum using zirconium tetra- tert-butoxide as precursor. Deposition of a > 50 Å thick film leads in both cases to tetragonal ZrO 2 ( t-ZrO 2), whereas significant differences are found for thinner films. On Si(1 1 1)-(7 × 7) the local structure of t-ZrO 2 is not observed until a film thickness of 51 Å is reached. On Si(1 0 0)-(2 × 1) the local geometric structure of t-ZrO 2 is formed already at a film thickness of 11 Å. The higher tendency for the formation of t-ZrO 2 on Si(1 0 0) is discussed in terms of Zr–O valence electron matching to the number of dangling bonds per surface Si atom. The Zr–O hybridization within the ZrO 2 unit depends furthermore on the chemical composition of the surrounding. The precursor t-butoxy ligands undergo efficient C–O scission on Si(1 0 0), leaving carbonaceous fragments embedded in the interfacial layer. In contrast, after small deposits on Si(1 1 1) stable t-butoxy groups are found. These are consumed upon further deposition. Stable methyl and, possibly, also hydroxyl groups are found on both surfaces within a wide film thickness range.