The luminescence arising in Cf 252-fission fragment induced desorption events has been measured using the time-correlated single photon counting technique. Photons emitted from the sample have been guided from a plasma desorption ion source to a photodetector by an optical fibre. Spectra and decay functions have been obtained using thin layers of Coronene or POPOP as samples. The results are strongly dependent on the acceleration field applied for ion extraction. Approximately 10 photons per fission fragment have been produced when applying no accelerating voltage. The results clearly show that these photons come from radiative electronic relaxations of molecules in the solid sample. Considerably more photons per fission fragment have been produced when applying a positive acceleration voltage. The intensity increases almost linearly for acceleration fields below 10 kV/cm and saturates at a nearly 10-fold higher value when compared to no acceleration. The intensity is also affected by the homogeneity of the accelerating field. These additional photons are attributed to radiative electronic relaxations of desorbed neutral molecules in the plume excited by inelastic collisions with accelerated positive ions. No additional photons have been observed when extracting negative ions. The negative ions produced do obviously not hit and/or excite desorbed neutral molecules, presumably due to their specific desorption characteristics. The experimental data have been analyzed by comparing with the cw and time-resolved sample luminescence obtained by optical excitation.The findings demonstrate that valuable information on ion-solid interactions, on specific desorption quantities and on processes in the plume can be obtained by measuring and analyzing the luminescence induced by the impact of high energy primary ions.