We report the photoassisted low‐temperature (LT) metalorganic chemical vapor deposition (MOCVD) of high resistivity GaAs. The undoped as‐grown GaAs exhibits a resistivity of ∼106 Ω cm, which is the highest reported for undoped material grown in the MOCVD environment. Photoassisted growth of doped and undoped device quality GaAs has been achieved at a substrate temperature of 400 °C in a modified atmospheric pressure MOCVD reactor. By using silane as a dopant gas, the LT photoassisted doped films have high levels of doping and electron mobilities comparable to those achieved by MOCVD for growth temperatures, Tg≳600 °C.