Metal chelates of three grades of carboxymethyl cellulose (CMC) (LI-L3) with Cu(II) ions, either originating from CuCl2or CuSO4, were prepared and characterized by elemental analysis, infrared spectra, and electrical conductivity studies. The results showed that the degree of substitution of CMCs and the origin of the Cu(II) ion have a profound effect on the amount of metal included in the polymer complexes and the structure and the electrical conductivity of the prepared complexes. CMC acts as a uninegatively charged bidentate ligand when it is chelated with Cu(II) of CuCl2via the carboxymethyl group and exhibits the formula Cu(L)2, whereas it acts as a binegatively charged bitentate ligand when it is chelated with CuSO4via the carboxymethyl and secondary hydroxyl groups and exhibits the formula CuL.2H2O. The investigation revealed that the electrical conductivity depends on the temperature and has two maximum peaks. The values of the activation energy for the conductivity of CMC and their complexes indicated that the samples changed from a low-semiconductor to a high-semiconductor property with heating. It is found that CMC-Cu(II) complexes formed from CuSO4exhibit a high-semiconductor property compared to complexes derived from CuCl2.