Direct reactions under ambient conditions between CuX (X = Br, I) and thiobenzamide (TBA) were carried out at different ratios, giving rise to the formation of a series of one-dimensional (1D) coordination polymers, (CPs) [CuI(TBA)](n) (1), [Cu3I3(TBA)(2)](n) (4), and [CuBr(TBA)](n) (5), as well as two molecular complexes, [CuI(TBA)(3)] (2) and [Cu2I2(TBA)(4)]center dot 2MeCN (3). Recrystallization of 1 and 5 yielded a series of isostructural 1D CP solvated species, [CuI(TBA)center dot S](n)](n) (1.S; S = tetrahydrofuran, acetone, methanol) and [CuBr(TBA)center dot S](n) (5.S; S = tetrahydrofuran, acetone), respectively. Similar reactions between CuI and 1,4-dithiobenzamide (DTBA) allowed the isolation of a series of two-dimensional (2D) CPs [CuI(DTBA)center dot S](n) (6.S; S = N,N-dimethylformamide, acetonitrile, methanol). Interestingly, 1.S and 5.S showed variable luminescence and electrical semiconductivity depending on the different solvents located in their structures. Thus, 1 and 5 could display potential application for sensing volatile organic vapors by virtue of the significant changes in their emission upon solvent exposure, even by the naked eye. Theoretical calculations have been used to rationalize these electronic properties.