Thermal decomposition of cesium azide (CsN3) leaves elemental cesium behind, which was in‐situ produced and used for the syntheses of the two new cesium thiotellurates Cs2[TeS2] and Cs2[TeS3] along with appropriate amounts of tellurium and sulfur. The first compound crystallizes orthorhombically in space group Cmc21 with the lattice parameters a = 783.39(4), b = 1126.72(8), c = 823.04(5) pm (Z = 4) and the second one monoclinically in space group P21/n with the lattice parameters a = 997.12(6), b = 1269.71(8), c = 1410.23(9) pm, β = 91.218(3)° (Z = 8). While ψ1‐tetrahedral complex thiotellurate(IV) anions [TeS3]2– are found as pyramids in Cs2[TeS3], Cs2[TeS2] comprises ψ2‐tetrahedral thiotellurate(II) units [TeS2]2– as boomerangs and both occur isolated in the corresponding structures. In each of the title compounds, the anionic part of the structures is arranged layer‐like with Cs+ cations sitting in between the layers. The cesium cations in the sulfur‐rich compound Cs2[TeS3] exhibit coordination numbers of seven and eight, while in the Cs2[TeS2] these cations are surrounded by only six sulfide anions. But even the lone‐pair electrons at the central Te4+ and Te2+ cations help to complete the Cs+ coordination spheres in both cases.