Li2GeTeO6 prepared at ambient pressure adopts the corundum derivative ordered ilmenite structure (rhombohedral R3). When heated at 1073 K and 3-5 GPa, the as-made Li2GeTeO6 can convert into a LiSbO3-derived Li2TiTeO6-type phase (orthorhombic Pnn2), which is the third LiSbO3-derived double A2BB'O6 phase in addition to Li2TiTeO6 and Li2SnTeO6. This Pnn2 Li2GeTeO6 phase spontaneously reverts to the R3 phase if annealed up to 1023 K at ambient pressure. Although the crystal structural analyses and second harmonic generation measurements clearly demonstrate the polar nature of both the R3 and Pnn2 phases, P( E) and dielectric measurements do not show any convincing ferroelectric response. Given the large estimated spontaneous polarization (17 and 80 μC/cm2), the absence of ferroelectric behavior could be attributed to the random domain distribution and leakage due to Li-ion migration.