This study presents high-performance intrinsically stretchable organic photovoltaics (IS-OPVs) with an initial power conversion efficiency (PCE) of 14.2%, exceptional stretchability (maintaining 80% of initial PCE at 52% tensile strain), and cyclic mechanical durability (retaining 95% of initial PCE after 100 strain cycles at 10%). The stretchability is achieved by redistributing strain in the active layer to a highly stretchable PEDOT:PSS electrode, which is enhanced by incorporating the zwitterion ION E. This strategy improves the stretchability of PEDOT:PSS and strengthens its interfacial adhesion with the polyurethane substrate, ensuring mechanical durability and delaying crack initiation and propagation in the top active layer. The study also introduces a new active system, Ter-D18:Y6, which achieves high PCE and superior mechanical properties. The IS-OPVs demonstrate excellent performance under high tensile strains and repetitive strain cycles, with a record-high stretchability of 52% PCE retention at 52% strain. The device design strategy is not solely dependent on the mechanical properties of the active layer, offering potential for various other active systems. The results highlight the importance of interfacial adhesion and strain redistribution in achieving high-performance stretchable OPVs.This study presents high-performance intrinsically stretchable organic photovoltaics (IS-OPVs) with an initial power conversion efficiency (PCE) of 14.2%, exceptional stretchability (maintaining 80% of initial PCE at 52% tensile strain), and cyclic mechanical durability (retaining 95% of initial PCE after 100 strain cycles at 10%). The stretchability is achieved by redistributing strain in the active layer to a highly stretchable PEDOT:PSS electrode, which is enhanced by incorporating the zwitterion ION E. This strategy improves the stretchability of PEDOT:PSS and strengthens its interfacial adhesion with the polyurethane substrate, ensuring mechanical durability and delaying crack initiation and propagation in the top active layer. The study also introduces a new active system, Ter-D18:Y6, which achieves high PCE and superior mechanical properties. The IS-OPVs demonstrate excellent performance under high tensile strains and repetitive strain cycles, with a record-high stretchability of 52% PCE retention at 52% strain. The device design strategy is not solely dependent on the mechanical properties of the active layer, offering potential for various other active systems. The results highlight the importance of interfacial adhesion and strain redistribution in achieving high-performance stretchable OPVs.