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Exploration of novel biaryls consisting of two polycyclic aromatic hydrocarbon (PAH) units can be an important strategy toward further developments of organic materials with unique properties. In this study, 5,5′‐bibenzo[rst]pentaphene (BBPP) with two benzo[rst]pentaphene (BPP) units is synthesized in an efficient and versatile approach, and its structure is unambiguously elucidated by X‐ray crystallography. BBPP exhibits axial chirality, and the (M)‐ and (P)‐enantiomers are resolved by chiral high‐performance liquid chromatography and studied by circular dichroism spectroscopy. These enantiomers have a relatively high isomerization barrier of 43.6 kcal mol⁻¹calculated by density functional theory. The monomer BPP and dimer BBPP are characterized by UV‐vis absorption and fluorescence spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. The results indicate that both BPP and BBPP fluoresce from a formally dark S₁electronic state that is enabled by Herzberg–Teller intensity borrowing from a neighboring bright S₂state. While BPP exhibits a relatively low photoluminescence quantum yield (PLQY), BBPP exhibits a significantly enhanced PLQY due to a greater S₂intensity borrowing. Moreover, symmetry‐breaking charge transfer in BBPP is demonstrated by spectroscopic investigations in solvents of different polarity. This suggests high potential for singlet fission in suchπ‐extended biaryls through appropriate molecular design.