We suggest a novel route for the preparation of organic conductive polymer composites that are doped by the programmable controlled dispersion of nickel-nanoclusters into a polymer matrix having structure of layer-by-layer. The layered structures of polyaniline composites containing nickel-nanoclusters (PANI-Ni) were prepared electrochemically by a two-pot process in 0.1 M H2SO4 and 0.5 M NiSO4. We discuss on what is intrinsic nature of the mutual influences of the PANI chains and nickel-nanoclusters within a PANI-Ni film, on the change in structural morphology, and on the broadening and shifts of anodic waves to higher potentials during cyclic voltammetry. Also the role of nickel-nanoclusters as a source supplying protons to promote the protonation to form polaron and bipolaron charge carriers of PANI was suggested. (C) 2005 Elsevier Ltd. All rights reserved.