[Co(en)3](Ti2F11) containing H-bonded assembly of a discrete cobaltammine complex cation and titanium fluoride anion was successfully synthesized under solvothermal conditions. A novel photoelectronic effect was observed in the near-UV region. By extending our understanding of this compound, taking into account our previously reported three cobalt complex-containing zirconium fluorides, the mechanism of photoelectronic effects from these molecular solids was determined by investigating the relative work function for their component species with the help of a Scanning Kelvin probe. The results suggest that the charge transfer from the excited cobaltammine complex cations to the metal fluoride anions as a result of the cooperative behaviors might occur upon illumination, which is responsible for these novel photoelectronic effects.