Photodetectors have widespread applications in fields including telecommunications, thermal imaging and bio-medical imaging. The photogating effect, arising from charge trapping at defects and/or interfaces, can have extremely high photoelectric gain which can be a benefit to high-sensitivity room temperature photodetection. Here, we introduce thin layered organic charge transfer complexes (CPXs) integrated on graphene transistors for the development of hybrid phototransistors with ultra-high photoresponsivity of ∼106 A W-1 in the near infrared (NIR) region at room temperature. Our study has demonstrated a graphene-organic CPX with a broadband photoresponse ranging from the visible to the NIR region. The high photoelectric gain was from the photogating effect at the graphene/CPX interface. In addition, the photoresponse properties of the graphene-organic CPX can be regulated by electrical gating of graphene.