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Three novel 1-D coordination polythiometalates have been synthesized and characterized by single-crystal X-ray crystallography, and their electrical properties have been studied. Compound {[W4Ag6S16]·[Ca(DEAC)6]}n, 1 crystallizes in the mono- clinic space group P21/n with a=13.769(3), b=11.613(2), c=24.153(5) A, β=96.31(3)°, V=3838.7(13) A, and Z=2 with R(wR2)=0.0607(0.1338), the polymeric anions in 1 feature a novel hanging ladder-like polymeric chain which can also be described as double helical chains bridged by silver atoms. Both compounds {[W2Ag2S8]·[Zn(4,4′-bipy)2(DMF)2(DMSO)2]}n 2 and {[W2Ag2S8]·[Zn(4,4′-bipy)2(DMSO)4]·(DMSO)}n 3 are composite polymers which consist of polymeric cations as well as polymeric anions. In 2, two polymeric chains simultaneously exist in the cell unit, one is the zigzag anionic chain, the other is the linear cationic chain. 2 crystallizes in the monoclinic space group C2/c with a=8.996(2) A, b=21.728(4) A, c=21.560(4) A, β=94.00(3)°, V=4204(2) A3, and Z=8 with R(wR2)=0.0546(0.1556). The difference between 2 and 3 is that the latter has a linear anionic chain and a zigzag cationic chain. X-ray crystallography established the monoclinic space group C2/c with a=28.8896(2), b=11.9395(1), c=16.2341(2) A, β=122.932(1)°, V=4699.82(8) A3, and Z=8 with R(wR2)=0.0438(0.1166)·4.50×10−6 S cm−1, respectively. Room temperature conductivities of 1, 2 are 2.92×10−5. Thus, compounds 1 and 2 have semiconductor electrical properties.