New germanium chalcogenide precursors, S═Ge(dmamp)2 (3), S═Ge(dmampS)2 (4), Se═Ge(dmamp)2 (5), Se═Ge(dmampS)2 (6), Te═Ge(dmamp)2 (7), and Te═Ge(dmampS)2 (8), were synthesized from Ge(dmamp)2 (1) and Ge(dmampS)2 (2) using sulfur, selenium, and tellurium powders (dmamp = 1-dimethylamino-2-methyl-2-propanolate, dmampS = 1-dimethylamino-2-methylpropane-2-thiolate). Complexes 1 and 2 were synthesized from metathesis reactions of GeCl2·dioxane with 2 equiv of aminoalkoxide or aminothiolate ligands. Thermogravimetric analysis of complex 1 displayed good thermal stability and volatility. The molecular structures of complexes 2-8 from X-ray single crystallography showed distorted trigonal bipyramidal geometry at the germanium centers. Germanium chalcogenide materials (GeSe and GeTe) were obtained from the thermal decomposition of complexes 5, 6, and 8 in hexadecane. X-ray diffraction patterns exhibited that GeSe and GeTe had orthorhombic and rhombohedral phases, respectively. This study affords a facile method to easily prepare germanium chalcogenide materials using well-designed and stable complexes by thermal decomposition of single-source precursors in solution.