Tri(9-anthryl)bismuthines 3 and their difluorobismuth derivatives 4 have been synthesized and their UV−visible absorptionspectra have been determined. The change from the tricoordinate 3 to the pentacoordinate 4 causes a subtle blue-shift in the λ0-0 of the anthryl moieties due to the decreased intramolecular through-space interaction between the anthryl moieties. Among the compounds, tri(9-anthryl)difluorobismuth