The metalorganic chemical vapor deposition (MOCVD) of epitaxial III‐V semiconductor alloys on III‐V substrates is reviewed in detail. The emphasis is placed on both practical and theoretical knowledge of the equipment and deposition process. The chemistry of the source alkyls and the dynamics of the transport process are discussed. The growth of the GaAs and AlxGa1−xAs systems are treated as prototypical examples (and the most studied) of the III‐V materials. Latter sections review InP, Ga1−xInxAs, and related alloys. Finally, the antimonide and the other systems are reviewed. Electronic and optical devices fabricated from MOCVD‐grown materials are used as examples of the capabilities of the growth technique.