A series of new hybrid selenidostannates [Mn(en)2(hda)]2[Sn2Se6](1, en = ethylenediamine, hda = N-(2-hydroxyethyl)ethylenediamine), [Ni(teta)(en)][Ni(teta)(hda)][Sn4Se10] (2, teta = triethylenetetramine), [Mn(hda)2]n[SnMnSe4]n (3), [Mn(dien)2]n[SnMnSe4]n (4, dien = diethylenetriamine), and [Zn2(en)2(μ4-SnSe4)]n (5) were solvothermally synthesized in hda solvent and structurally characterized. 1 is composed of a discrete [Sn2Se6]4- anion and a complex [Mn(en)2(hda)]2+ cation as the counterion. 2 contains the [Ni(teta)(en)]2+ ion, [Ni(teta)(hda)]2+ ion and [Sn4S10]4- adamantane-like ion built from the corner-sharing connection of four [SnSe4]4- tetrahedra, which offers the rare example of hybrid selenidostannate combined with two different types of transition metal complexes as counterions. Both 3 and 4 contain a 1-D heterometallic [SnMnSe42-]n anionic chain constructed from [Sn/MnSe4] tetrahedra sharing opposite edges, whose Sn4+ and Mn2+ ions are situated at the same site in the lattice, but their chains exhibit two different configurations. 5 exhibits a new type of 2-D organic-decorated [Zn2(en)2(μ4-SnSe4)]n layer incorporating rare tetrahedral [ZnSe2(en)] complexes. Their optical and photocurrent response properties were studied, and density functional theory calculations for 5 were also performed.