Superconducting Tl2CaBa2Cu2Oythin films have been successfully grown on the single‐crystal sapphire (11¯02) substrate by using the metalorganic chemical vapor deposition technique. The growth rate of the films was about 5 &mgr;m/h. The as‐deposited film was post‐annealed in a partially sealed ceramic crucible in the presence of a Tl2Ca2Ba2Cu3Oypellet to achieve the superconducting phase. The x‐ray data show strong diffraction from the Tl2CaBa2Cu2Oysuperconducting phase in addition to the trace amounts of Ca2CuO3and BaCO3. Superconducting transition temperatures with onset above 100 K and zero resistance at 94 K can be obtained by further heat treatment at 500 °C in oxygen.