Two semiconducting hybrid gallium selenides, [Ga6Se9(C6H14N2)(4)] [H2O] (1) and [C6H14N2][Ga4Se6(C6H14N2)(2)] (2), were prepared using a solvothermal method in the presence of 1,2-diaminocyclohexane (1,2-DACH). Both materials consist of neutral inorganic layers, in which 1,2-DACH is covalently bonded to gallium. In 1, the organic amine acts as a monodentate and a bidentate ligand, while in 2, bidentate and uncoordinated 1,2-DACH molecules coexist.