Abstract New lanthanide-selenidostannate complexes [{La(peha)(Cl)}{La(peha)(NO3)}(μ-1κ2:2κ2-SnSe4)] (1), [H2trien][{La(trien)2}2(μ-1κ:2κ-Sn2Se6)][Sn2Se6]·H2O (2) and [{Ln(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)] n ·nH2O (Ln=Sm(3), Eu(4)) were prepared by solvothermal methods in pentaethylenehexamine (peha), triethylenetetramine (trien) and tetraethylenepentamine (tepa), respectively. Acting as a tetradentate chelating and bridging ligand, μ-1κ2:2κ2-SnSe4, the tetrahedral SnSe4 unit joins {La(peha)(Cl)}2+ and {La(peha)(NO3)}2+ complex fragments to generate the neutral coordination compound 1. The tetradentate μ-1κ2:2κ2 bridge in 1 represents a new coordination mode for the SnSe4 tetrahedron. In 2, dinuclear [Sn2Se6]4− anions are formed of SnSe4 tetrahedra via edge-sharing. One [Sn2Se6]4− anion acts as a bidentate bridging ligand in a μ-1κ:2κ coordination mode to join two {La(trien)2}3+ units, and the other [Sn2Se6]4− anion exists as a free charge compensating ion. In 3 and 4, the [Sn2Se6]4− anion connects binuclear [{Ln(tepa)(μ-OH)}2]2+ (Ln=Sm, Eu) units with a bidentate μ-1κ:2κ mode, giving neutral coordination polymers [{Ln(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)] n . The La(2)3+ ion in 1 is in a 10-fold coordination environment of LaN6O2Se2, whereas the La(1)3+ ions in 1 and 2 are in 9-fold coordinated environments forming polyhedra LaN6ClSe2 and LaN8Se, respectively. The Sm3+ and Eu3+ ions in 3 and 4 are both in an 8-fold coordination environment of LnN5O2Se. Compounds 1−4 exhibit optical band gaps between 2.21 and 2.42 eV. Their thermal stabilities were investigated by thermogravimetric analyses.