The substituted pyrrole monomer, N–(2–cyanoethyl)pyrrole, was electropolymerised in a 70% water and 30% ethanol solution with ClO4– and H2PO4– as the dopant species to give nanowires at short electropolymerisation times and microwires at longer deposition periods. On adding toluene to the electropolymerisation solution, hollow microtubes were formed. This was attributed to the adsorption of toluene droplets at the electrode surface which served to separate the dopants from the monomer, with the monomer being highly soluble in the toluene droplet and the inorganic dopants soluble in the water/ethanol mixture. As a result electropolymerisation was confined to the toluene-water/ethanol interface. These polymer systems exhibit redox activity with the oxidation wave centred at about 0.40 V vs SCE, and the broader reduction wave positioned between 0.75 V and 0.25 V vs SCE. Although N-substitution reduces the conductivity of the polymer, various copper deposits, including cubes, leaves and hierarchical structures were deposited at the microwires and microtubes using high overpotentials. The hierarchical structures were wrapped around the microtubes at considerable distances, typically 3–4 µm, from the substrate.