Poly(vinyl chloride) (PVC) has been reacted with dimethylglyoxime (DMG) in THF to form the PVC–DMG comples, which has been characterized by spectroscopic and elemental analyses. The latter indicate that there is one DMG moiety anchored on the PVC chain by displacing every 12th Cl atom in the chain. PVC–DMG has further been reacted with alcoholic solutions of Co(II), Ni(II), and Cu(II) to form the intensely colored PVC–DMG–M(II) complexes. The structures of these complexes have been analyzed by elemental and IR spectral analyses. The overall thermal stability of PVC–DMG–M(II) increases in the order: PVC < PVC–DMG–Cu(II) < PVC–DMG–Ni(II) < PVC–DMG–Co(II). The electrical conductivities are also significantly enhanced in the same order. The permittivities of these complexes are high relative to PVC at low frequency falling gradually with increasing frequency and the dielectric loss-frequency behavior is very broad.