The pseudo-binary line of Sb2Te3-GeTe contains alloys featuring different crystalline characteristics from two-dimensionally (2D-) bonded Sb2Te3 to three-dimensionally (3D-) bonded GeTe. Here, the growth scenario of 3D-bonded GeTe is investigated by depositing epitaxial GeTe thin films on Si(111) and Sb2Te3-buffered Si(111) substrates using pulsed laser deposition (PLD). GeTe thin films were grown in trigonal structure within a temperature window for epitaxial growth of 210–270 °C on unbuffered Si(111) substrates. An unconventional growth onset was characterized by the formation of a thin amorphous GeTe layer. Nonetheless, the as-grown film is found to be crystalline. Furthermore, by employing a 2D-bonded Sb2Te3 thin film as a seeding layer...