Remarkable progresses regarding pure inorganic frameworks and metal-organic frameworks (MOF) have been made. However, pure inorganic frameworks with MOF-like grid structures are rarely reported due to the weakness of inorganic moiety as a long linear linker. We report herein a fascinating inorganic framework assembled by a [Ge4S10](4-) cluster node and a linear [-Cu-MS4-Cu-] (M = Mo (1) and W (2)) inorganic pillar. Their network shows MOF-like orthogonal structure with two interpenetrated two-dimensional (2D) plus 2D to 3D framework and a 1D nano tunnel. Electrodes with crystalline sample of 1 and 2, inorganic sulfide framework, were prepared, and their quasi-capacitance behaviors were investigated. Electrochemical performances were evaluated by cyclic voltammetry and galvanostatic charge-discharge techniques in CsOH, KOH, NaOH, and LiOH electrolytes. The results revealed that the crystal materials exhibit moderate specific capacitance values that are comparable to those of porous sulfide materials.