High surface area metal electrodes are desirable for applications in energy storage and energy conversion. Here, the formation and electrochemical characterization of a hybrid material made by electroless deposition of gold onto a scaffolding of vertically aligned carbon nanofibers is described. Vertically aligned carbon nanofibers, similar to 80 nm in diameter, provided mechanical support and electrical contact to the highly textured nanoscale gold coatings. By chemically functionalizing the nanofiber surfaces and then using electroless deposition methods, a highly textured metal coating was formed. The electrochemical response of these "nano-on-nano" hybrid electrodes was characterized using electrochemical methods. The results show that using the metallic coatings can increase the electrochemically active surface area by up to a factor of 10 compared with the starting carbon nanofiber scaffolds. The electrochemical response of the electrodes was modulated by varying the deposition time of the gold. (C) 2011 Elsevier B.V. All rights reserved.