The paper describes the time-dependent evolution of the electrochemical deposition of cobalt hexacyanoferrate (CoHCFe) on graphite foil electrode modified with electrochemically formed sol–gel film doped with β-cyclodextrin to impart porosity. With short-time electrodeposition, cyclic voltammetry (CV) shows a single redox couple typical of nano-sized clusters of CoHCFe, while at longer deposition times the CV’s shape evolves to the classical form of a bulk compound in which there are present two redox couples. The electrode modified with β-cyclodextrin (CD) included in the sol–gel film has an active surface that corresponds to pores created by CD stacks normal to the surface. Hence, the electrochemical formation of CoHCFe starts in these conductive pores; only at long deposition times do the clusters overlap to form moieties with the voltammetric characteristics of bulk CoHCFe.