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A Prussian blue (PB) film was deposited on a glassy carbon (GC) electrode by cyclic voltammetry in the presence of the cationic surfactant cetyltrimethylammonium bromide (CTAB). The electrode thus formed showed 4-fold enhancements in redox current and charge values in pure KCl electrolyte as well as greater stability than an electrode prepared in the absence of CTAB. This improved performance of a PB+CTAB electrode versus a PB electrode was further demonstrated using SEM, XRD, and electrochemical impedance spectroscopy (EIS) measurements. A comparative study was undertaken on the cation transport characteristics of PB and PB+CTAB electrodes for Na+, Li+, and NH4+ ions. We obtained a CV pattern for a CTAB-promoted PB film, which showed ideal Nernstian behavior at all scan rates from 5 to 140 mV s(-1). Conditions for the formation and preservation of these ideal and stable PB films are discussed. Possible mechanisms for the beneficial effects of CTAB are proposed.