Rigid‐Isomer‐Controlled Pressure Locking of Synergistic Optoelectronic Enhancement in 1D Hybrid Perovskites

High‐performance optoelectronic materials inherently struggle to simultaneously optimize luminescence and photocurrent, particularly in low‐dimensional hybrid perovskites. Although high‐pressure modulation can optimize the optoelectronic properties of materials, conventional flexible organic cations are prone to conformational relaxation, resulting in inefficient stress transmission, uncontrolled structural modulation and the inability to retain high‐pressure properties. To address this, we leverage the conformational differences between the syn ‐ and anti ‐isomers of 3,3′‐bipyridine to design and synthesize a pair of rigidity‐differentiated one‐dimensional (1D) perovskites, ( syn ‐3,3′‐H 2 bpy)PbBr 4 and ( anti ‐3,3′‐H 2 bpy)PbBr 4 . This enables the precise manipulation of inorganic framework distortions and interfacial coupling under high pressure. Our investigations reveal that the more rigid anti ‐cations ensure efficient stress transmission, achieving a breakthrough of generating photocurrent from an initially insulating state, alongside an average 392‐fold photoluminescence enhancement, which is a record for 1D organic–inorganic hybrid perovskites under high pressure. Upon decompression, these pressure‐optimized structures are successfully intercepted, enabling the synchronized enhancement of luminescence and photocurrent at ambient pressure that breaks their intrinsic performance contradiction. By realizing the precise customization of pressure‐responsive behaviors through molecular configurational rigidity modulation, this work provides a reliable structural design basis for overcoming the performance trade‐off in optoelectronic materials and developing high‐performance, multifunctional perovskite optoelectronic devices.