The sp3 C–H acetoxylation at the β-position of α,α-disubstituted α-amino acids proceeds smoothly under palladium catalysis in presence PhI(OAc)2. This reaction provides a straightforward synthetic route to non-natural β-acetoxy-α-amino acids. α-aminocyclopropanecarboxylic acid takes place via ring-opening selectively afford an acyclic γ-acetoxy-α,β-unsaturated amino acid.