Boosting Intrinsic Chirality of One‐dimensional Perovskite Single Crystals via Extended Cation Conjugation

ABSTRACT Chiral hybrid perovskites exhibit great potential in chiral optoelectronics, but suffer from insufficient intrinsic chirality due to inefficient chirality induction from the organic cation. Here, we unravel that extending the conjugation length of organic cation enhances the intrinsic chirality of 1D chiral hybrid perovskite single crystals (CHPSCs). The extended conjugation length of organic cation intensifies the inorganic‐framework torsion and regulates the band‐edge configuration through improved hydrogen bonding and π‐electron interactions, thereby strengthening intrinsic crystalline chirality. Benefiting from the superior intrinsic chirality and intensified intermolecular interaction, the 1‐(1‐naphthyl)ethylammonium (NEA) based 1D CHPSC achieves a high circularly polarized photocurrent anisotropy factor of 0.38 with a specific detectivity of 1.03 × 10 ¹¹ Jones. Furthermore, it is experimentally found that the 1D CHPSC inherits the same structural asymmetry from its corresponding chiral ligand, enabling actual chirality transfer. This study provides deeper insight into advancing the intrinsic chirality of CHPSCs for high‐performance optoelectronic applications.