We describe the modification of a glassy carbon electrode by electro-deposition of copper hexacyanoferrate (CuHCF) in the presence of an amine-terminated dendrimer (PAMAM) as a template. The electrode containing the CuHCF template was cycled in alkaline solution to generate a layer of cupric oxide (CuO). The mechanism of the formation of CuO and its electrocatalytic activity were investigated by cyclic voltammetry. Scanning electron microscopy reveals that the CuO prepared by this method has a meso-porous grid-like appearance. The formation of CuO was identified by XPS analysis of the modified electrode. The ability of the CuHCF film towards the electrocatalytic oxidation of carbohydrates and alcohols was detected using cyclic voltammetry. The over-potential required for carbohydrate and alcohol oxidation is lowered by ~400 mV compared to other chemically modified electrodes reported in the literature. Simple methodology has been adopted in this work for the preparation of the catalytically active electrode, and this work also explains the structure directing effect of dendrimer and its influence on the electrocatalytic oxidation of analytes.