Two new alkali metal germanophosphates, namely, Na₃[Ge(OH)(PO₄)₂]·2H₂O and Li₂Na[GeO(HPO₄)(PO₄)], have been prepared by solvothermal method, and their crystal structures were determined by single-crystal X-ray diffraction. The title two compounds crystalize in the same orthorhombic space group Pbcm (No. 57) and feature similar chain-like structure which is built from zig-zag GeO₆ octahedral thread loop branched by PO₄ tetrahedra. For Na₃[Ge(OH)(PO₄)₂]·2H₂O, a = 10.1650(9), b = 13.1975(12), c = 6.9751(7) Å, V = 935.73(15) ų, Z = 4, R = 0.0356 and wR = 0.1109; and for Li₂Na[GeO(HPO₄)(PO₄)], a = 6.9855(5), b = 14.5809(18), c = 6.6620(5) Å, V = 678.56(11) ų, Z = 4, R = 0.0286, and wR = 0.0762. The partial substitution of Na ions by Li ions not only significantly influences the total structural features and the water molecule contents, but also impacts on their thermal stabilities. Li₂Na[GeO(HPO₄)(PO₄)] is thermally stable up to 400 ℃, whereas only 150 ℃ for Na₃[Ge(OH)(PO₄)₂]·2H₂O.