Polyphenol is electropolymerized on a Au electrode in the presence of N,N'-dimethyl-4,4'-bipyridinium, methyl viologen, MV2+, to yield an imprinted film for MV2+. The association and dissociation of MV2+ to and from the imprinted sites is studied by electrochemical means and compared to the interactions of MV2+ with the non-imprinted polymer. Donor-acceptor interactions provide the driving force for the formation of the imprinted sites. The imprinted polymer reveals selectivity toward the association of MV2+,, and the polymer-bound MV2+ enables vectorial electron transfer between the electrode and redox label dissolved in the bulk electrolyte solution.