A novel perylene imide and oligo-pentaphenyl bisfluorene containing molecule is shown to undergo electron transfer to form an emissive charge transfer state in di-benzyl ether and THF. At the single molecule level in a PMMA film, fluorescence spectra characteristic of both emissive states (locally excited and charge transfer) are observed with 44% of the molecules studied showing switching between the two states. These results demonstrate that charge transfer fluorescence from single molecules can be used to report on the properties and dynamics of a molecule’s immediate surroundings or nano-environment.