The scandium oxodiselenate(IV) Sc 2 [Se 2 O 5 ] 3 was synthesized via solid-state reactions between scandium sesquioxide (Sc 2 O 3 ) and selenium dioxide (SeO 2 ) with thallium(I) chloride (TlCl) as fluxing agent in molar ratios of 1:4:2. Evacuated fused silica ampoules were used as reactions vessels for annealing the mixtures for five days at 800 • C. The new scandium compound crystallizes in the triclinic space group P1 with the lattice parameters a = 663.71(5) pm, b = 1024.32 (7) pm, c = 1057.49 (8) pm, α = 81.034(2) • , β = 87.468(2) • , γ = 89.237(2) • and Z = 2. There are two distinct Sc 3+ positions, which show six-fold coordination by oxygen atoms as [ScO 6 ] 9− octahedra (d(Sc-O) = 205-212 pm). Three different [Se 2 O 5 ] 2− anions provide these oxygen atoms with their terminal ligands (O t ). Each of the six selenium(IV) central atoms exhibit a stereochemically active lone pair of electrons, so that all [Se 2 O 5 ] 2− anions consist of two ψ 1 -tetrahedral [SeO 3 ] 2− subunits (d(Se-O t ) = 164-167 pm, d(Se-O b ) = 176-185 pm, (O-Se-O) = 93-104 • ) sharing one bridging oxygen atom (O b ) with (Se-O b -Se) = 121-128 • . The vibrational modes of the complex anionic [Se 2 O 5 ] 2− entities were characterized via single-crystal Raman spectroscopy.