Abstract: A series of 10,10-dioctyl-3,6-dihydrofluoreno[2,3-d:6,7-d′]diimidazole derivatives were conveniently synthesized by condensation of the key intermediate 2,3,6,7-tetraamino-9,9-dioctylfluorene (TADOF) with aldehydes under very mild conditions. All of the target compounds were characterized using 1H NMR, 13C NMR, and elemental analysis. The crystal structure of 3,6-dibenzyl-10,10-dioctyl-2,7-diphenyl-6,10-dihydro-3H-fluoreno[2,3-d:6,7-d′]diimidazole was determined as triclinic, space group P-1 type, using single X-ray crystallography. For seventeen samples, UV–visible absorption maximum wavelength (λ max), fluorescence excitation wavelength (λ ex), fluorescence emission wavelength (λ em) and fluorescence quantum yield (φ FL) were measured in dilute dichloromethane solution and in the solid state. These compounds possess a medium strong blue fluorescence-emitting ability with φ FL values in the region of 0.30–0.89 and structure-optical behavior characteristics were discussed. [Copyright &y& Elsevier]