The construction and performance of a novel electrochemical (EC) surface plasmon resonance (SPR) instrument based on a mini three electrode flow cell that was designed and manufactured by MEMS technology is described. The working electrode is 50nm gold and counter and reference electrodes, made of Au and Ag/AgCl separately, are 0.6 mm in diameter. The flow channel is made of polydimethylsiloxane (PDMS) with 1mm in width, 200μm in depth, 5μL in volume. The process for activating and modifying the working electrode is given by the real-time SPR detection. The Cyclic voltammetry (CV) and SPR detection are conducted simultaneously in potassium ferricyanide solution system. It is proved that the signal of redox reaction and the change of refractive index have a well correlation by the potential sweep experiment. Four kinds of concentration of potassium ferricyanide are analyzed and the peak oxidizing current, obtained from the curve, is proportional to the respective concentration of the sample. The EC-SPR experiment is also carried out in CuSO4 system and the results is similar to potassium ferricyanide.