Variations of the GaAs surface conditions and the adsorption of the precursor elements of Cd and Te on the (100)GaAs substrate were studied by x‐ray photoelectron spectroscopy at the initial stage of CdTe growth by organometallic vapor phase epitaxy. The stoichiometry of GaAs substrates was found to recover by annealing in the H2environment (500 °C, 5 min), while the surface was initially in an As‐rich condition after etching with H2SO4:H2O2:H2O (5:1:1). The preferential adsorption of Te on the GaAs surface was also observed. ⟨100⟩ oriented growth was obtained routinely when the GaAs surface was fully stabilized with Te after the H2anneal under the above conditions. ⟨111⟩ oriented growth resulted when dimethylcadmium was first introduced after the anneal.