The growth of GeTe thin films on a Si(111)-(√3 × √3)R30°-Sb surface is reported. At growth onset, the rapid formation of fully relaxed crystalline GeTe(0001)-(1 × 1) is observed. During growth, a GeTe(0001)-(√3 × √3)R30° surface reconstruction is also detected. Indeed, density functional theory (DFT) simulations indicate that the reconstructed GeTe(0001)-(√3 × √3)R30° structure is energetically competing with the GeTe(0001)-(1 × 1) reconstruction. The out-of-plane α-GeTe||Si and in-plane α-GeTe||Si epitaxial relationships are confirmed by X-ray diffraction (XRD). Suppression of rotational twist and reduction of twinned domains are achieved. The formation of rotational domains in GeTe grown on Si(111)-(7 × 7) is explained by domain matched coincidence lattice formation with the Si(111)-(1 × 1) surface. Atomic force microscopy (AFM) images show the coalescence of well …