We report the first electrochemical method to prepare Au-containing nanocomplexes with controllable particle size via roughening gold substrates with oxidation-reduction cycles (ORC) of various scans in 0.1 N KCl aqueous solutions without the addition of any stabilizer. The prepared nanocomplex size increases from 2 to 50 nm with the increase of the ORC scan from 25 to 400 cycles. Furthermore, polypyrrole, (PPy)-coated gold nanocomposites can be synthesized by the formation of self-assembled layers and further autopolymerization of pyrrole monomers on these nanocomplexes, caused by their activities.