Photoemission spectroscopy is used to demonstrate that Ge segregates to the first atomic layer of Ge0.5Si0.5(100)2×1 and that the second layer is predominantly Si. Comparison of the resolved signals from the dimer atoms of the reconstructed (100)2×1 surfaces of Ge, Si, and equiatomic Ge‐Si alloy shows that the surface layer of the alloy is extremely Ge rich and the second layer is occupied mainly by Si atoms. This result is in good agreement with theoretical predictions.