Electrodes modified with metal hexacyanoferrates find a unique place in the contemporary electrochemistry in view of their multifarious applications. The modification of carbon substrates with thin films of zinc hexacyanoferrate (ZnHCF) is reported for the first time. Stable surface modification is favoured when the Zn2+/Fe(CN)(3-)(6) ratio is 1:1, while deviation from this ratio leads to interesting electrocrystallisation phenomena. K+ ion has a facile entry and exit into the lattice of ZnHCF compared to other cations such as Na+,Li+, NH4+ etc.