In this study, a dual rotating-disk photocatalytic fuel cell using TiO2 on Ti plate with a wedged surface as the anode and hemoglobin (Hb) on graphite as the cathode was investigated and found to show excellent performance of simultaneous organic pollutant degradation and electricity generation. This study is based on a well-developed photocatalytic fuel cell equipped with dual rotating disks for wastewater treatment that we developed previously, and the innovation of this new device is using a hemoglobin on graphite cathode for in situ hydrogen peroxide (H2O2) generation. The result proved with confidence that H2O2 was generated in situ on a cathode surface with the exited electron transferred from organic oxidation in a photoanodic half cell, and the organic pollutants were removed by the reaction with H2O2 and OH in a cathodic half cell. This design uses the invalid excited electron from the photoanode and enhances the overall performance of Rhodamine B degradation compared with the cells using the cathode without Hb. Compared with traditional photocatalytic reactors, the photocatalytic fuel cell developed above shows much better utilization efficiency of incident light and a higher degradation performance of organic pollutants and a larger photocurrent.