Amphiphilic discotic pentakis(arylethynyl) benzene compounds 1 and 2 containing an enlarged aromatic core functioning as a chromophoric pi-electron system were studied with regard to their photophysical properties within Langmuir-Blodgett (LB) films. The results obtained from steady-state absorption as well as fluorescence excitation and emission measurements will be discussed with regard to interchromophoric interactions in the LB films. Time-resolved fluorescence investigations revealed the formation of a ground-state complex as well as excimer formation. Thermal treatment causes irreversible destruction of the LB film structure of the discotic amphiphiles. Within droplets the reorganization of the original nematic-discotic (N-D) mesophase of the bulk materials was found for the alcohol 2 as indicated by a Maltese Cross texture, whereas the acid 1 remained isotropic.