Anhydrous compounds are crucially important for many technological applications, such as achieving high performance in lithium/sodium cells, but are often challenging to synthesize under hydrothermal conditions. Herein we report that a modified solvo-/ hydro-fluorothermal method with fluoride-rich and water-deficient condition is highly effective for synthesizing anhydrous compounds by the replacement of hydroxyl groups and water molecules with fluorine. Two anhydrous phosphate germanium fluorides, namely, Na-3[GeF4(PO4)] and K-4[Ge2F9(PO4)], with chainlike structures involving multiple fluorine substitutions, were synthesized using the modified solvo-/hydro-fluorothermal method. The crystal structure of Na-3[GeF4(PO4)] is constructed by the common single chains infinity(1){[GeF4(PO4)](3-)} built from alternating GeO2F4 octahedra and PO4 tetrahedra. For K-4[Ge2F9(PO4)], it takes the same single chain in Na-3[GeF4(PO4)] as the backbone but has additional flanking GeOF5 octahedra via an O-corner of the PO4 groups, resulting in a dendrite zigzag single chain infinity(1){[Ge2F9(PO4)](4-)}. The multiple fluorine substitutions in these compounds not only force them to adopt the low-dimensional structures because of the "tailor effect" but also improve their thermal stabilities. The thermal behavior of Na-3[GeF4(PO4)] was investigated by an in situ powder X-ray diffraction experiment from room temperature to 700 degrees C. The modified solvo-/hydro-fluorothermal method is also shown to be effective in producing the most germanium-rich compounds in the germanophosphate system.