Gold bead electrodes were modified with submonolayers of 3-mercaptopropionic acid or 2-aminoethanethiol and further reacted with poly(amidoamine) (PAMAM) dendrimers (generation 4.0 and 3.5, respectively) to obtain films on which Prussian Blue (PB) was later absorbed to afford mixed and stable electrocatalytic layers. Experiments carried out with these novel materials not only showed an improved surface coverage of PB on the dendrimer modified electrodes as compared to PB modified gold electrodes prepared under acidic conditions, but also showed an increased stability at neutral pH values for one of the dendrimer containing substrates where the PB film on a bare gold electrode is simply not formed. The dendrimer modified electrodes were also tested as electrocatalytic substrates for the electroxidation of L(+)-ascorbic acid (AA), and it was found that their sensitivity as well as the corresponding detection limits were improved as compared to the voltammetric response of a Au-PB modified electrode. On the basis of LTV-visible (UV-vis) spectroscopy and electrochemical experiments, it is suggested that the PB molecules are located within the dendritic structure of the surface attached PAMAM dendrimers.