In this work, the reduction and oxidation capacities of organic supporting electrolytes for ferricenium (Fc(+)) and ferrocene (Fc) were investigated by micro and nano hybrid electrodes in this work. The Fc(+) can be produced in situ at the carbon electrode and collected simultaneously at the liquid/liquid (L/L) interface. The experiments were based on the generation/collection (G/C) technique and the redox capability of the supporting electrolytes was defined by the collection efficiency. Five common employed supporting electrolytes in the organic phase (TBADCC, TBATPB, TBATPBCI, TBATPBF and TBATPBF(5)) were discussed and the experimental results indicated that the reduction power of these supporting electrolytes was weakened successively. The oxidation ability of cations of some supporting electrolytes (TPAsTPBF5, TBATPBF(5) and BTPPATPBF(5)) were also tested using the same methodology, showing that TBA(+) and BTPPA(+) have little influence on this system in comparison with oxidation of Fc to Fc(+) by TPAs+. Besides, the different concentration of supporting electrolyte verse Fc was also studied to further prove the redox effect of supporting electrolytes on Fc(+).