The electrochemical behaviour of some Ni gamma-monosubstituted dibenzotetraaza [14] annulene complexes has been investigated. The oxidation in CH2Cl2 Of the complex containing a 4-carboxybenzyl group leads to the corresponding gamma-gamma dimer whose electrochemical properties have been studied. The electrode surface can be coated by thin films of this dimer using CH3CN instead of CH2Cl2; however, the resulting modified electrode is poorly stable. The oxidation of the complex containing 1-(4-carboxybenzyl)pyrrole as gamma substituent involves gamma-gamma dimer formation before the formation of a regular polypyrrole film. The film displays reversible electrochemical reduction of the metal centre (Ni(II)/Ni(I)) and two successive oxidations of the macrocycle (Mc/Mc.+ and MC.+/MC2+). The complex containing a bromo(4-carboxybenzyl) group offers an unusual feature in that polymeric films can be obtained following an original procedure based on alternated dimerizations. This is a consequence of the formation of two different dimers obtained by anodic and cathodic processes.