Two Λ-shaped BODIPY dyes based on Tröger's base, 2,8-(6H,12H-5,11-methanodibenzo[b,f]diazocineylene)-di(4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene) (DFTMB) and 2,8-(6H,12H-5,11-methanodibenzo[b,f]diazocineylene)-di(4,4-difluoro-2,6-diethyl-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene) (DFDEB), were designed and synthesized. Both compounds exhibit intense fluorescence in dilute solution and polycrystalline powder form. From the crystal structure, the impact of the substitutions at the BODIPY core on the crystal packing mode, intermolecular π–π interactions and optical behavior is compared and discussed. The results indicate that the close π–π stacking in the crystalline state has been effectively inhibited by the twisted Λ-shaped Tröger's base.