Electrochemical behavior of dopamine (DA) and ascorbic acid (AA) at dendritic Au rod (DAR) surfaces prepared by a simple and fast electrodeposition from sulfite-based Au(I) electrolytes was investigated. The unique DAR structures with sharp edge Au sites differentiated the anodic waves between DA and AA, and the electrooxidation of DA at DAR surfaces was significantly enhanced at lower DA concentration ranges. The DAR surfaces enabled the differential pulse voltammetric determination of DA in the presence of 0.1 mM of AA, and the modification of the DAR with Nafion layer; enhanced the sensitivity and selectivity against AA. Electrochemical deposition would offer an efficient route for fabricating nanostructured surfaces for electrochemical determination of biologically important species. (C) 2012 Elsevier B.V. All rights reserved.