The surface electrochemistry of polypyrrole–polystyrene sulfonate (PPy–PSS) thin films is exploited for the fabrication of novel hybrid copper-based microstructures. The electrochemical deposition of the copper-based materials at the PPy–PSS film is strongly dependent on the electrode potential. This dependence is studied at three different potentials: 0.10, 0.00, and −0.10 V vs SCE. Hierarchical micro/nanostructures made of copper hydroxysulfate salts are only formed at 0.10 V vs SCE and are replaced with branched and single microcrystals of Cu2O covered by a thin layer of Cu(OH)2 at 0.00 and −0.10 V vs SCE, respectively. The different structures can be coupled on the same film through a simple fabrication procedure to give hybrid microstructures. These novel hybrids consist of a central microcrystal (deposited at −0.10 V vs SCE) and a surrounding contour of welded nanosheets (deposited at 0.10 V vs SCE). The mechanism of nucleation and growth of the hierarchical micro/nanostructures formed at 0.10 V vs SCE is also reported. These structures are made from the assembly of nanoparticles into nanowires, nanosheets, and microclusters. These microclusters have a flowerlike shape within which each nanosheet forms a petal of the flower. The nucleation of the clusters is shown to be progressive.