Neuromorphic computing, reconfigurable optical metamaterials that are operational over a wide spectral range, holographic and nonvolatile displays of extremely high resolution, integrated smart photonics, and many other applications need next-generation phase-change materials (PCMs) with better energy efficiency and wider temperature and spectral ranges to increase reliability compared to current flagship PCMs, such as Ge2Sb2Te5 or doped Sb2Te. Gallium tellurides are favorable compounds to achieve the necessary requirements because of their higher melting and crystallization temperatures, combined with low switching power and fast switching rate. Ga2Te3 and non-stoichiometric alloys appear to be atypical PCMs; they are characterized by regular tetrahedral structures and the absence of metavalent bonding. The sp3 gallium hybridization in cubic and amorphous Ga2Te3 is also different from conventional p-bonding in flagship PCMs, raising questions about its phase-change mechanism. Furthermore, gallium tellurides exhibit a number of unexpected and highly unusual phenomena, such as nanotectonic compression and viscosity anomalies just above their melting points. Using high-energy X-ray diffraction, supported by first-principles simulations, we will elucidate the atomic structure of amorphous Ga2Te5 PLD films, compare it with the crystal structure of tetragonal gallium pentatelluride, and investigate the electrical, optical, and thermal properties of these two materials to assess their potential for memory applications, among others.