Ternary metal-oxy-chalcogenides are emerging as next-generation layered semiconductors beyond binary metal-chalcogenides (i.e., MoS2). Among ternary metal-oxy-chalcogenides, especially Bi2O2Se has been demonstrated in field-effect transistors and photodetectors, exhibiting ultrahigh performance with robust air stability. The growth method for Bi2O2Se that has been reported so far is a powder sublimation based chemical vapor deposition. The first step for pursuing the practical application of Bi2O2Se as a semiconductor material is developing a gas-phase growth process. Here, we report a cracking metal–organic chemical vapor deposition (c-MOCVD) for the gas-phase growth of Bi2O2Se. The resulting Bi2O2Se films at very low growth temperature (∼300 °C) show single-crystalline quality. By taking advantage of the gas-phase growth, the precise phase control was demonstrated by modulating the partial pressure of each precursor. In addition, c-MOCVD-grown Bi2O2Se exhibits outstanding electrical and optoelectronic performance at room temperature without passivation, including maximum electron mobility of 127 cm2/(V·s) and photoresponsivity of 45134 A/W.