Prussian blue modified electrodes derived from Fe[Fe(CN)(5)adpy] (adpy = isonicotinamide) exhibit reversible electrochemical waves at E1/2 = 0.45 and 1.1V vs. she, ascribed to the FeIII/II and [Fe(CN)5adpy](2-/3-) redox couples, respectively. Reversible electrochromic behavior is observed below 0.7 V, associated with the rise and decay of the intervalence band at 775nm. The resonance raman spectra of the modified electrodes are dominated by the vibrational peaks of the isonicotinamide ligand; in contrast, the SERS spectra exhibit only metal-CN vibrational peaks, suggesting an adsorption mechanism involving the cyanide ligands. The electrodes based on the Ni-x[Fe(CN)(5)adpy](y) analogue exhibit reversible waves at 0.5 and 0.7V, ascribed to [Fe(CN)(5)adpy](3-) species located in non-equivalent sites. These sites exhibit a contrasting response for K+ and Na+ ions.