Suppressing nonradiative recombination at the interface between the organometal halide perovskite (PVK) and the charge-transport layer (CTL) is crucial for improving the efficiency and stability of PVK-based solar cells (PSCs). Here, a new bathocuproine (BCP)-based nonconjugated polyelectrolyte (poly-BCP) is synthesized and this is introduced as a "dual-side passivation layer" between the tin oxide (SnO<sub>2</sub> ) CTL and the PVK absorber. Poly-BCP significantly suppresses both bulk and interfacial nonradiative recombination by passivating oxygen-vacancy defects from the SnO<sub>2</sub> side and simultaneously scavenges ionic defects from the other (PVK) side. Therefore, PSCs with poly-BCP exhibits a high power conversion efficiency (PCE) of 24.4% and a high open-circuit voltage of 1.21 V with a reduced voltage loss (PVK bandgap of 1.56 eV). The non-encapsulated PSCs also show excellent long-term stability by retaining 93% of the initial PCE after 700 h under continuous 1-sun irradiation in nitrogen atmosphere conditions.