A portable litmus-type chemosensor is developed for the effective detection of environmentally hazardous volatile organic compounds (VOCs) using polydiacetylene (PDA) and graphene stacked within a composite film. The graphene is exploited as a transparent and efficient supporter for the highly ordered PDA monolayer. This colorimetric sensor exhibits a sensitive response to low concentrations of VOCs (∼0.01%), including tetrahydrofuran (THF), chloroform (CHCl3), methanol (CH3OH), and dimethylformamide (DMF). The color change that is caused by relatively high concentrations of VOCs can be perceived by the naked eye, and it is noteworthy that a logarithmic relationship is observed between the chromatic response and the VOC concentration in the range of ∼0.01%–10%. The structural conformation changes of the PDA molecules, caused by interactions with VOCs, are directly observed by scanning tunneling microscopy (STM), which reveals the intrinsic mechanism of the chromatic variety at the molecular level.