The surface structures that result from the adsorption of Te on (100) GaAs have been shown to affect the orientation of CdTe films on GaAs. Two structures are described here. A low‐temperature (6×1) surface leads to (100) film growth. At 580 °C, a new surface results which is characterized by ordering along directions 60° from [011¯] and [01¯1], and leads to (111) growth of CdTe. Both surface structure and the interaction of the group II element with the surface are believed to be important in determining the orientation of the film.