High throughput, sharp interfaces, and selective deposition with direct ion‐, electron‐, and photon‐beam‐controlled techniques are some of the key driving forces for the development of superconducting thin films by the metalorganic chemical vapor deposition technique. In this paper, we report on theinsitudeposition of a buffer layer of BaF2and high‐temperature superconducting thin films of Y‐Ba‐Cu‐O by metalorganic chemical vapor deposition (MOCVD) on silicon substrates. These films have an on‐set temperature of 90 K and zero resistance at 73 K. The use of BaF2as a buffer layer on Si substrates suggests the possibility of three‐dimensional integration with high‐temperature superconducting thin films, for hybrid superconductor/semiconductor devices as well as superconducting switches and other related devices. To the best of our knowledge, this is the first report of the deposition of high‐temperature superconducting thin films on Si by MOCVD.