The charge transfer characteristics of molecular hetero-LB films composed of green fluorescence protein (GFP), viologen, and cytochrome-c were investigated by transient fluorescence measurement. In this work, transient fluorescence decay of GFP homo film and GFP/viologen/cytochrome-c hetero films were measured to investigate the charge separation rate and transport mechanism by using time-correlated single photon counting method (TCSPC).