The six new bis(4-cyano-1-pyridino)alkanes derivatives with different alkyl chain length (n = 2-6) and cyanometallate anions ([Fe(CN)(6)](3) , [Co(CN)(6)](3) , [Fe(CN)(4)(CNH)(2)](2) and [Fe(CN)(6)](4) ) have been synthesized and characterized by 1H-NMR, single-crystal X-ray analysis and UV-vis spectroscopy. The electroreduction of the obtained compounds under potentiostatic conditions (E-1 = -0.75 V) and further electrode stabilization at E-2 = 0V resulted in the deposition of polyviologen films. The current efficiency of electropolymerization was found to increase with varying the counter anion in the row: [Fe(CN)(6)](3) < Br < [Co(CN)(6)](3) similar to [Fe(CN)(6)](4) . Analysis of cyclic voltammograms and EDX data demonstrated the simultaneous incorporation of [Fe(CN)(6)](4) and K+ ions into poly(pentyl-viologen) film during electropolymerization, and further expulsion of K+ ions during the film stabilization at E-2 = 0V. The electropolymerization efficiency was found to increase with increasing the alkyl chain length, resulting in the formation of polyviologen film with higher content of dimer form of viologen cation radical. (C) 2016 Elsevier Ltd. All rights reserved.