Monolayers of three new biferrocene derivatives (BiFc) containing an alpha,beta-unsaturated carbonyl group have been investigated and a stable Langmuir monolayer of each BiFc was formed at the air-water interface. The mixed monolayer of each BiFc with arachidic acid (AA) is easily assembled to Langmuir-Blodgett (LB) films. The UV-Vis spectra indicate that an H-aggregate is formed in mixed LB films. The surface morphology of each kind of mixed LB monolayer has been detected by scanning electron microscopy and phase separation has been observed. The electrochemical redox reaction of Fe(CN)(6)(3-)/Fe(CN)(6)(4-) could be catalyzed by the indium tin oxide electrodes modified with the mixed monolayer of BiFc and AA.