The chalcogenides Cs 2 CdGeSe 4 (1), Cs 2 Hg 2 GeSe 5 (2), and Na 3 RbCu 8 Ge 3 S 12 (3) were synthesized by solvothermal condition. Germanium chalcogenides containing transition metals have flexible crystal structures. Compound 1 has a one-dimensional (1-D) chain structure consisting of anionic chain ∞ 1 {[GeCdSe 4 ] 2− } and Cs + cations. Compound 2 is a zero-dimensional (0-D) cluster structure consisting of anionic clusters of [GeHgSe 5 ] 2−and Cs + cations. Compound 3 is a three-dimensional (3-D) network structure consisting of a copper-rich [Cu 8 Ge 3 S 12 ] 4− anion and Na + and Rb + cations. Transition metal compounds with inorganic frameworks have abundant optical and electrical properties. We explored the photocurrent response of compounds 1−3. There are remarkable photocurrent densities for compounds 1−3, especially 1 with a density of 180 μA/cm 2 , which is superior to most germanium chalcogenides.