Development of ecofriendly and low-cost highly efficient photocatalysis is of importance in the field of chemical synthesis. Currently, various metals-based organic materials, metal oxide nanoparticles, and metal nanomaterials have been urbanized as light harvesting photocatalysts for direct carbon (C)-hydrogen (H) arylation of aryl diazonium salts and heteroarenes. These light harvesting photocatalysts, however, still suffer from poor stability, reusability problem, high cost, or less selectivity. Herein, we report the fabrication of a novel chitosan-based fluorescein isothiocyanate (CBFITC) film photocatalyst and demonstrate its tremendous photocatalytic activity, high yields (97 +/- 0.015%), selectivity (99%), and reusability to catalyze the metal free solar-light-mediated direct C-H arylation of aryl diazonium salts and heteroarenes at ambient temperature. Moreover, CBFITC film photocatalyst can be recycled more than five times without loss of activity, verifying this photocatalyst excellent light harvesting ability and stability. The present approach to fabricate a metal-free film photocatalyst with the suitable band gap will be a new platform for efficient photocatalytic reaction and provide a new insight into the solar chemical synthesis.