Ultrathin oxides have been reported to possess excellent properties in electronic, magnetic, optical, and catalytic fields. However, the current and primary approaches toward the preparation of ultrathin oxides are only applicable to amorphous or polycrystalline oxide nanosheets or films. Here, we successfully synthesize high-quality ultrathin antimony oxide single crystals via a substrate-buffer-controlled chemical vapor deposition strategy. The as-obtained ultrathin antimony oxide single crystals exhibit high dielectric constant (~100) and large breakdown voltage (~5.7 GV m-1). Such a strategy can also be utilized to fabricate other ultrathin oxides, opening up an avenue in broadening the applicaitons of ultrathin oxides in many emerging fields.