Films of the highTcBi‐Sr‐Ca‐Cu‐O superconductor have been prepared by organometallic chemical vapor deposition using the volatile metalorganic precursors Cu(acetylacetonate)2, Sr(dipivaloylmethanate)2, and Ca(dipivaloylmethanate)2, and triphenylbismuth. Deposition is carried out at 2 Torr with argon as the carrier gas and oxygen and water vapor as reactants. Film growth rates of 2–3 &mgr;m/h are achieved. After annealing under oxygen, energy dispersive x‐ray analysis and x‐ray diffraction data reveal that such films on [100] single‐crystal MgO consist predominantly of the Bi2(Sr,Ca)3Cu2Ox,Tc=85 K, phase and have preferential orientation of the crystallitecaxes perpendicular to the substrate surface. Four‐probe resistivity measurements reveal the onset of film superconductivity at ∼110 K and zero resistance by 75 K.