The visible light-operated biomass-O2 biofuel cell consisting of chlorin-e6 (Chl-e6) adsorbed on nanocrystalline TiO2 layer coated onto optical transparent conductive glass electrode (OTE) as an anode, platinum coated OTE as a cathode, and the solution containing starch (polysaccharide biomass), glucoamylase, glucose dehydrogenase (GDH) and NAD+ as a fuel is studied. as a new type fuel cell. The short-circuit photocurrent (ISC) and the open-circuit photovoltage (VOC) of this cell are 13.0 micro-A cm-2 and 610 mV, respectively. Thus, a new type of visible light-operated starch-O2 biofuel cell with the visible photosensitization of Chl-e6 molecules on nanocrystalline TiO2 film electrode is accomplished.