Fabrication of highly ordered conducting polymers on metal surfaces has received a significant interest owing to their potential applications in organic electronic devices. In this context, we have developed a simple method for the synthesis of highly ordered polypyrrole (PPy) on copper modified aluminium surfaces via electrochemical polymerization process. A series of characteristic peaks of PPy evidenced on the infrared spectra of these surfaces confirm the formation of PPy. The X-ray diffraction (XRD) pattern of PPy deposited on copper modified aluminium surfaces also confirmed the deposition of PPy as a sharp and intense peak at 20 angle of 23 attributable to PPy is observed while this peak is absent on PPy deposited on as-received aluminium surfaces. An atomic model of the interface of PPy/Cu has been presented based on the inter-atomic distance of copper-copper of (1 0 0) plane and the inter-monomer distance of PPy, to describe the ordering of PPy on Cu modified Al surfaces. 2014 Elsevier B.V. All rights reserved.