The reaction of copper with molten alkali polytelluride salts led to several novel compounds with a characteristic structural feature based on a pentagonal dodecahedral geometric solid. We report here in detail the synthesis, structure, and chemical, spectroscopic, and charge-transport properties of K4Cu8Te11, A(3)Cu(8)Te(10), and A(2)BaCu(8)Te(10) along with electronic band structure calculations on the two-dimensional Cu8Te10 framework. K4Cu8Te11 is monoclinic C2/m with a = 24.086(3) Angstrom, b = 6.821(6) Angstrom, c = 18.461(3) Angstrom, beta = 124.45(1)degrees, V = 2501 Angstrom(3) at 23 degrees C, Z = 4, no. of data used (I > 3 sigma(I)) 2029, no. of variables 121. The final R/R(w) was 2.5%/3.7%. Rb3Cu8Te10 is monoclinic C2/m with a = 24.420(11) Angstrom, b = 6.974(6) Angstrom, c = 6.933(1) Angstrom, beta = 104.90(1)degrees, V = 1141 Angstrom(3) at 23 degrees C, Z = 2, no. of data used (I > 3 sigma(I) 721, no. of variables, 57 final R/R(w) 5.7%/7.3%. Cs3Cu8Te10 is orthorhombic Immm with a = 7.053(2) Angstrom, b = 24.159(3) Angstrom, c = 6.935(3) Angstrom, V = 1182 Angstrom(3) at 23 degrees C, Z = 2, no. of data used (I > 3 sigma(I)) 839, no. of variables 36 final R/R(w) 3.2%/5.0%. K0.9Cs2.1Cu8Te10 is orthorhombic 6) Angstrom, c = 6.908(3) Angstrom, V = 1159 Angstrom(3) at 23 degrees C, Z = 2 no. of data used (I > 3 sigma(I)) 625, no. of variables 37, final R/R(w) 3.5%/3.0%. K2BaCu8Te10 is monoclinic C2/m with a = 23.245(5) Angstrom, b = 6.950(5) Angstrom, c = 7.061(5) Angstrom, beta = 101.23(4)degrees, V = 1119 Angstrom(3) at 23 degrees C, Z = 2, no. of data used (I > 3 sigma(I)) 1445, no, of variables 57, final R/R(w) 8.8%/11.3%. Cs2BaCu8Te10 is orthorhombic Immm with a = 7.109(2) Angstrom, b = 23.761(16) Angstrom, c = 6.966(3) Angstrom, V = 1177 Angstrom(3) and Z = 2, no. of data used (I > 3 sigma(I)) 795, no. of variables 35, final R/R(w) 3.0%/6.0%.