Perovskite defects are a major hurdle in the efficiency and stability of perovskite solar cells (PSCs). While various defect passivation materials have been explored, most are insulators that hinder charge transport. This study investigates the potential of two different pi-conjugated polyelectrolytes (CPEs), MPS2-TEA and PCPDTBT2-TMA, as semiconducting additives in PSCs. The CPEs differ in electrical conductivity, offering a unique approach to bridge defect mitigation and charge carrier transport. Unlike previous uses of CPEs mainly as interlayers or charge transport layers, we explore their direct effect on defect passivation within a perovskite layer. Secondary ion microscopy reveals the even distribution of CPEs within the perovskite layer and their efficient defect passivation potential is studied through various spectroscopic analyses. Comparing MPS2-TEA and PCPDTBT2-TMA, we find MPS2-TEA to be superior in defect passivation. The highly conductive nature of PCPDTBT2-TMA due to self-doping diminishes its defect passivation ability. The negative sulfonate groups in the side chains of PCPDTBT2-TMA stabilize polarons, reducing defect passivation capability. Finally, the PSCs with MPS2-TEA achieve remarkable power conversion efficiencies (PCEs) of 22.7% for 0.135 cm(2) and 20.0% for large-area (1 cm(2)) cells. Furthermore, the device with MPS2-TEA maintained over 87.3% of initial PCE after 960 h at continuous 1-sun illumination and 89% of PCE after 850 h at 85 degrees C in a nitrogen glovebox without encapsulation. This highlights CPEs as promising defect passivation additives, unlocking potential for improved efficiency and stability not only in PSCs but also in wider applications.