Ta 2P 2S 11 is a new phase of the TaPS system obtained by high-temperature synthesis from the elements. Single-crystal diffraction analysis showed the phase to crystallize in the P2 1 c space group with the following cell parameters: a = 6.876(3), Å, b = 24.109(8)Å, c = 26.411(8), Å, β = 106.04(3)°, V = 4208(6), Å 3, and Z = 10. Low-temperature ( T = 140 K) structure study has been performed and 3104 independent diffractometer data have been refined, with 328 variables, to R = 8.9%. The structure is made of two types of polyhedra, a tetrahedral group (PS 4) (mean d PS = 2.030, Å) and a bipolyhedral group (Ta 2S 11) (mean d TaS = 2.494, Å) in which tantalum is heptacoordinated. These (Ta 2S 11) units are formed of two distorted (TaS 7) groups sharing a triangular face made of mono- and disulfide anions ((S 2) −IIS −II). Of the three kinds of (Ta 2S 11) bipolyhedra, two of them show disorder of the common triangular sulfur face. The way the coordination groups are bonded to one another determines the occurrence of three kinds of tunnels in the structure. Their characteristics and the reason of their emptiness are related to their size and to the special linking arrangement taking place between the (PS 4) and (Ta 2S 11) groups. With the formulation Ta V 2P V 2(S 2) −II(S −II) 9 the phase is expected to be diamagnetic and semiconducting or insulator.