Most of the group 5 metal chalcogen-rich ternary M/Q/X system (M = Nb, Ta; Q = S, Se; X = Cl, Br) have been reported to have low-dimensional structures and interesting properties induced by the low-dimensional nature. 1-5 The structures of these compounds are usually composed of one-dimensional chains in which the metal atoms are arranged in waved distributions with sequences of short and long intermetallic distances. The metal atoms are connected through disulfides (S 2 2− ) and sulfide anions and various metal-centered polyhedra play roles as basic structural building blocks. The intermetallic distances vary and diversified structures can be obtained from the various combinations of metals and bridging anions. Most of the compounds in this family have been prepared from the mixtures of elements. However, in our group, reactive halide flux technique has been used to prepare many new metal chalcogenides and chalcogenophosphates. This synthetic route has proved to be of general utility in preparing new multinary chalcogenides. [5][6][7][8][9][10][11] In an attempt to search for new phases in the Ag-Nb-V-S system using eutectic halide fluxes, we have found a new one-dimensional niobium sulfide chloride. Here we report the synthesis and structural studies of Nb 24 S 95 Cl 7 .The structure of Nb 24 S 95 Cl 7 is composed of three crystallographically independent one-dimensional chains extended along the [110] direction. (Figure 1) The chains have similar shapes and all of them are comprised of alternating clusters made from three and five Nb atoms. The three-and five-membered linear clusters are constructed from two and four consecutive short intermetallic bonds (Nb-Nb: 2.9220 (6)~3.1394(6) Å, Table 1), respectively. Each cluster is connected by bridging S atoms to form one-dimensional chains. (Figure 2) The coordination around the terminal Nb atoms of the clusters is responsible for the different structure of the chains. In the type I chain, 1 ∞ [Nb 8 S 32 Cl 2 ], only the terminal Nb atoms (Nb(1), Nb(3)) of the threemembered cluster have Cl ions and the type II chain,