The electrochemical behavior of potassium ferrocyanide [K4Fe(CN)(6)] at Pt/ionic liquid (IL) microemulsion interfaces was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). H2O/TX-100/bmimPF(6) was used to prepare three IL microemulsions: water in 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)) (W/IL), bicontinuous (WIL) and bmimPF(6) in water (IL/W). The results show that the IL microemulsion systems have relatively narrower potential windows compared with the pure IL system. The redox potential gap is about 100 mV in the pure water and the three IL microemulsions. The redox potentials of K4Fe(CN)(6)/K3Fe(CN)(6) and the redox peak currents decrease in the order pure water, IL/W, WIL, W/IL. Furthermore, the peak currents increase linearly with the square root of the scan rate, while the diffusion coefficient increased in the order W/IL, WIL, IL/W. The Nyquist plots obtained in the WIL and IL/W systems show capacitive resistance arcs at high frequencies and 45A degrees straight lines at low frequencies, implying that the electrochemical reactions are controlled by charge transfer and diffusion steps. For the W/IL system there is only a 45A degrees straight line in the Nyquist plot, indicating that diffusion is the controlling step at all frequencies.