The new charge neutral complex [Cr(tren)SbS3]·H2O was synthesized under solvothermal conditions applying CrCl3·6H2O, Sb2S3, and S as starting material in an aqueous tren solution (tren = tris(2‐aminoethyl)amine)). The compound crystallizes in the non‐centrosymmetric space group P212121with a = 8.7779(15), b = 10.7122(17), c = 15.4286(18) Å, V = 1450.8(4) Å3. In the structure the Cr3+ion is surrounded by four N atoms of the amine molecules and by two S atoms of a trigonal pyramidal [SbS3]3−group, i.e., the latter acts as a bidentate ligand. A three‐dimensional network is formed via hydrogen bonds between the complexes and water molecules. The main resonances in the Raman spectrum can be explained on the basis of calculated data. The most intense band is due to the Sb‐S stretching vibration. The thermal properties were investigated by DTA‐TG measurements. On heating [Cr(tren)SbS3]·H2O decomposes in two distinct steps. The first step corresponds to the removal of the water molecules and the second step to the loss of the tren ligand.